WO2014158395A1 - Functionalized polymers containing polyamine succinimide for demulsification in hydrocarbon refining processes - Google Patents
Functionalized polymers containing polyamine succinimide for demulsification in hydrocarbon refining processes Download PDFInfo
- Publication number
- WO2014158395A1 WO2014158395A1 PCT/US2014/015974 US2014015974W WO2014158395A1 WO 2014158395 A1 WO2014158395 A1 WO 2014158395A1 US 2014015974 W US2014015974 W US 2014015974W WO 2014158395 A1 WO2014158395 A1 WO 2014158395A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polypropylene
- mol
- branched
- propylene
- formula
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 108
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 59
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 57
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 54
- 229920000642 polymer Polymers 0.000 title description 86
- 229920000768 polyamine Polymers 0.000 title description 38
- 238000007670 refining Methods 0.000 title description 14
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 title description 8
- 229960002317 succinimide Drugs 0.000 title description 4
- 239000000839 emulsion Substances 0.000 claims abstract description 58
- 239000000654 additive Substances 0.000 claims abstract description 57
- 230000000996 additive effect Effects 0.000 claims abstract description 34
- -1 polypropylene Polymers 0.000 claims description 95
- 229920001155 polypropylene Polymers 0.000 claims description 87
- 239000004743 Polypropylene Substances 0.000 claims description 85
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 48
- 150000001875 compounds Chemical class 0.000 claims description 47
- 229910052739 hydrogen Inorganic materials 0.000 claims description 39
- 125000000217 alkyl group Chemical group 0.000 claims description 30
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 27
- 239000005977 Ethylene Substances 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 125000002947 alkylene group Chemical group 0.000 claims description 22
- 125000003342 alkenyl group Chemical group 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 239000004711 α-olefin Substances 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000003277 amino group Chemical group 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 description 95
- 229920001577 copolymer Polymers 0.000 description 50
- 239000008096 xylene Substances 0.000 description 49
- 150000003738 xylenes Chemical class 0.000 description 49
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 48
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 45
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 42
- 239000000463 material Substances 0.000 description 36
- 238000005160 1H NMR spectroscopy Methods 0.000 description 35
- 239000012299 nitrogen atmosphere Substances 0.000 description 33
- 239000000047 product Substances 0.000 description 32
- 239000003921 oil Substances 0.000 description 31
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 30
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 28
- 238000010438 heat treatment Methods 0.000 description 26
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 26
- 150000001336 alkenes Chemical class 0.000 description 24
- 150000008064 anhydrides Chemical class 0.000 description 24
- 238000000921 elemental analysis Methods 0.000 description 24
- 239000000243 solution Substances 0.000 description 23
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 20
- 229940014800 succinic anhydride Drugs 0.000 description 16
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 15
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 15
- 239000010779 crude oil Substances 0.000 description 14
- 229920002554 vinyl polymer Polymers 0.000 description 14
- 125000000746 allylic group Chemical group 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 239000007858 starting material Substances 0.000 description 13
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 12
- 238000000926 separation method Methods 0.000 description 12
- 0 C*(*N(C(CC1CC=C*)=O)C1=O)N(*)*N(*)* Chemical compound C*(*N(C(CC1CC=C*)=O)C1=O)N(*)*N(*)* 0.000 description 11
- 229940045348 brown mixture Drugs 0.000 description 11
- 238000009833 condensation Methods 0.000 description 11
- 230000005494 condensation Effects 0.000 description 11
- 150000003254 radicals Chemical class 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 10
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 10
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 10
- 239000003999 initiator Substances 0.000 description 9
- 239000002861 polymer material Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 8
- 239000012263 liquid product Substances 0.000 description 8
- 229920005606 polypropylene copolymer Polymers 0.000 description 8
- 239000007762 w/o emulsion Substances 0.000 description 8
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 6
- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical compound CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 6
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 6
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 6
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 6
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 6
- 229920002367 Polyisobutene Polymers 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 6
- 125000000623 heterocyclic group Chemical group 0.000 description 6
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 6
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 6
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- 238000011033 desalting Methods 0.000 description 5
- 238000007306 functionalization reaction Methods 0.000 description 5
- 229920005652 polyisobutylene succinic anhydride Polymers 0.000 description 5
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 101150090596 DMA2 gene Proteins 0.000 description 4
- 229920002873 Polyethylenimine Polymers 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical class ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229940126062 Compound A Drugs 0.000 description 3
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 229940069096 dodecene Drugs 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000011345 viscous material Substances 0.000 description 3
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 2
- QTYUSOHYEPOHLV-FNORWQNLSA-N 1,3-Octadiene Chemical compound CCCC\C=C\C=C QTYUSOHYEPOHLV-FNORWQNLSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 2
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 2
- 101150043088 DMA1 gene Proteins 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001414 amino alcohols Chemical class 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 2
- AQGNVWRYTKPRMR-UHFFFAOYSA-N n'-[2-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCNCCN AQGNVWRYTKPRMR-UHFFFAOYSA-N 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- 239000012434 nucleophilic reagent Substances 0.000 description 2
- 229920001281 polyalkylene Polymers 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- CHAYOQQPFPOYMD-PZORYLMUSA-N CC(C)[C@@H](CCC(C)(C)C(C)C)C(CC(O1)=O)C1=O Chemical compound CC(C)[C@@H](CCC(C)(C)C(C)C)C(CC(O1)=O)C1=O CHAYOQQPFPOYMD-PZORYLMUSA-N 0.000 description 1
- LSCFJXBYVYYZTB-YFKPBYRVSA-N CC(C)[C@H](CC(O1)=O)C1=O Chemical compound CC(C)[C@H](CC(O1)=O)C1=O LSCFJXBYVYYZTB-YFKPBYRVSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 229920002368 Glissopal ® Polymers 0.000 description 1
- 101001046633 Homo sapiens Junctional adhesion molecule A Proteins 0.000 description 1
- 102100022304 Junctional adhesion molecule A Human genes 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- GJTGYNPBJNRYKI-UHFFFAOYSA-N hex-1-ene;prop-1-ene Chemical class CC=C.CCCCC=C GJTGYNPBJNRYKI-UHFFFAOYSA-N 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000007723 transport mechanism Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- SXYOAESUCSYJNZ-UHFFFAOYSA-L zinc;bis(6-methylheptoxy)-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].CC(C)CCCCCOP([S-])(=S)OCCCCCC(C)C.CC(C)CCCCCOP([S-])(=S)OCCCCCC(C)C SXYOAESUCSYJNZ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
- C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/18—Use of additives to fuels or fires for particular purposes use of detergents or dispersants for purposes not provided for in groups C10L10/02 - C10L10/16
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1033—Oil well production fluids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
- C10L2230/08—Inhibitors
- C10L2230/086—Demulsifiers
Definitions
- the disclosed subject matter relates to additives to demulsify a hydrocarbon emulsion and methods and systems using the same.
- Desalting is one of the first steps in crude refining. This is done to remove salts and particulates to reduce corrosion, fouling and catalyst poisoning.
- fresh water is mixed with oil to produce a water-in-oil emulsion which in turn extracts salt and brine and some particulates from oil.
- the salty emulsion is then sent to a desalter unit where the application of an electric field forces water droplets to coalesce. Large electrocoalesced water droplets settle under gravity and separate from the desalted oil.
- Electrocoalescence i.e. coalescence under electric field
- demulsifiers are added to crudes and/or emulsions.
- the material properties of these demulsifiers allow them to remain in the oil phase of an emulsion.
- These additives reduce the emulsion stability, causing an enhancement in water separation, desalting and electrocoalescence and thus emulsion resolutions.
- the disclosed subject matter provides demulsifying chemical additives for treating a hydrocarbon emulsion. These additives can stay in the oil phase, and therefore can be added to a crude oil or emulsion as demulsifiers to enhance the desalting process.
- a method for treating an emulsion of a hydrocarbon includes: (i) providing an emulsion of a crude hydrocarbon, and (ii) adding an additive to the emulsion to obtain a treated hydrocarbon, the additive being represented by one of Formula A, B, C, and D below:
- n is an integer between 0 and 10 inclusive
- Ri is a branched or straight-chained Cio-Cgoo alkyl or alkenyl group
- R 2 is a C1-C4 branched or straight chained alkylene group
- R 3 is a C1-C4 branched or straight chained alkylene group
- R31 is hydrogen or -Rg-Rg, wherein Rg is C1-C4 branched or straight chained alkylene group, and R9 is
- R91 is a branched or straight-chained Cio-Cgoo alkyl or alkenyl group; or Rg and R9 together are a C1-C4 branched or straight chained alkyl group optionally substituted with one or more amine groups; and further wherein the -N(R 3 i)-R 3 - repeat unit is optionally interrupted in one or more places by a nitrogen-containing heterocyclic cycloalkyl group; and R4 and R 5 are each independently selected from (a) hydrogen; (b) a bond connected to R31 in the last distal -N(R 3 i)-R 3 - repeat unit; or (c) -R6-R7, wherein R 6 is C1-C4 branched or straight chained alkylene group, and R 7 is
- R 7 i is a branched or straight-chained Ci 0 -C 8 oo alkyl or alkenyl group
- n is an integer between 0 and 10 inclusive, and the groups R 2 ' , R 3 ', R 3 i ' , R4' and R 5 ' are each defined the same as R 2 , R 3 , R 3 i and R4, and R 5 , respectively;
- a method for preparing a compound for treating an emulsion of crude hydrocarbon in a hydrocarbon refining process includes:
- R 2 i is a branched or straight-chained Cio-Cgoo alkyl or alkenyl group
- Ri 2 is hydrogen or a C 1 -C 4 branched or straight chained alkyl optionally substituted with one or more amine groups
- R 13 is a C 1 -C 4 branched or straight chained alkylene group
- x is an integer between 1 and 10
- the -N(Ri 2 )-Ri 3 - unit is optionally interrupted in one or more places by a nitrogen-containing heterocyclic cycloalkyl group, and wherein when the x-th -N(Ri 2 )-Ri 3 - unit along with the terminal nitrogen atom forms a heterocyclic cycloalkyl group, the terminal -NH 2 is replaced by a -NH- group for valency.
- a method for preparing a compound of Formula D for treating an emulsion of crude hydrocarbon in a hydrocarbon refining process includes:
- R 2 i is a branched or straight-chained Cio-Cgoo alkyl or alkenyl group, z is 1 or 2, and y is an integer between 1 and 5 inclusive; (b) reacting the polymer obtained in a) with a polyamine represented by
- Ri 2 is hydrogen or a C 1 -C4 branched or straight chained alkyl optionally substituted with one or more amine groups
- R 3 is a C 1 -C4 branched or straight chained alkylene group
- x is an integer between 1 and 10
- the -N(Ri 2 )-Ri 3 - unit is optionally interrupted in one or more places by a nitrogen-containing heterocyclic cycloalkyl group, and wherein when the x-th -N(Ri 2 )-Ri 3 - unit along with the terminal nitrogen atom forms a heterocyclic cycloalkyl group, the terminal -NH 2 is replaced by a -NH- group for valency.
- compositions comprising such additives, and systems for refining hydrocarbons containing such additives and
- FIG. 1 is a representation of an oil refinery crude pre -heat train, annotated to show non-limiting injection points for the additives of the disclosed subject matter.
- FIG. 2 A is a plot illustrating the effects of an additive of the present application in treating an emulsion
- FIG. 2B show images of an emulsion as treated by the additive as compared with a control experiment.
- FIG. 3 is a plot illustrating the effects of various additives of the disclosed subject matter in treating an emulsion.
- the term "demulsifier” refers to a chemical suitable for addition crude oil to enhance the phase separation (for example, water separation) of a crude hydrocarbon emulsion in a refinery process, such as in a desalter or dehydrator.
- alkyl refers to a monovalent hydrocarbon group containing no double or triple bonds and arranged in a branched or straight chain.
- alkylene refers to a divalent hydrocarbon group containing no double or triple bonds and arranged in a branched or straight chain.
- alkenyl refers to a monovalent hydrocarbon group containing one or more double bonds and arranged in a branched or straight chain.
- hydrocarbyl group refers to any univalent radical that is derived from a hydrocarbon, including univalent alkyl, aryl and cycloalkyl groups.
- the term "crude hydrocarbon refinery component” generally refers to an apparatus or instrumentality of a process to refine crude hydrocarbons, such as an oil refinery process, which is, or can be, susceptible to fouling.
- Crude hydrocarbon refinery components include, but are not limited to, heat transfer components such as a heat exchanger, a furnace, a crude preheater, a coker preheater, or any other heaters, a FCC slurry bottom, a debutanizer exchanger/tower, other feed/effluent exchangers and furnace air preheaters in refinery facilities, flare compressor components in refinery facilities and steam cracker/reformer tubes in petrochemical facilities.
- Crude hydrocarbon refinery components can also include other instrumentalities in which heat transfer can take place, such as a fractionation or distillation column, a scrubber, a reactor, a liquid-jacketed tank, a pipestill, a coker and a visbreaker. It is understood that “crude hydrocarbon refinery components,” as used herein, encompasses tubes, piping, baffles and other process transport mechanisms that are internal to, at least partially constitute, and/or are in direct fluid communication with, any one of the above-mentioned crude hydrocarbon refinery components.
- reference to a group being a particular polymer encompasses polymers that contain primarily the respective monomer along with negligible amounts of other substitutions and/or interruptions along the polymer chain.
- reference to a group being a polypropylene group does not require that the group consist of 100% propylene monomers without any linking groups, substitutions, impurities or other substituents (e.g., alkylene or alkenylene substituents).
- Such impurities or other substituents can be present in relatively minor amounts so long as they do not affect the industrial performance of the additive, as compared to the same additive containing the respective polymer substituent with 100% purity.
- the olefin present in the polymer is the polymerized form of the olefin.
- a copolymer is a polymer comprising at least two different monomer units (such as propylene and ethylene).
- a homo-polymer is a polymer comprising units of the same monomer (such as propylene).
- a propylene polymer is a polymer having at least 50 mole%> of propylene.
- vinyl termination also referred to as “allyl chain end(s)” or “vinyl content” is defined to be a polymer having at least one terminus represented by: allylic vinyl end group
- allyl chain end is represented by:
- the amount of allyl chain ends (also called % vinyl termination) is determined using 1H NMR at 120°C using deuterated tetrachloroethane as the solvent on a 500 MHz machine and in selected cases confirmed by 13 C NMR.
- Isobutyl chain end is defined to be a polymer having at least one terminus represented by the formula:
- the "isobutyl chain end to allylic vinyl group ratio" is defined to be the ratio of the percentage of isobutyl chain ends to the percentage of allylic vinyl groups.
- polymer refers to a chain of monomers having a Mn of
- a method for treating an emulsion of a hydrocarbon includes: (i) providing an emulsion of a crude hydrocarbon, and (ii) adding an additive to the emulsion to obtain a treated hydrocarbon, the additive being represented by one or more of Formula A, B, C, and D below:
- n is an integer between 0 and 10 inclusive
- Ri is a branched or straight-chained Cio-Cgoo alkyl or alkenyl group
- R 2 is a C1-C4 branched or straight chained alkylene group
- R3 is a C1-C4 branched or straight chained alkylene group
- R31 is hydrogen or -Rg-Rsi, wherein R 8 is C1-C4 branched or straight chained alkylene group, and R 9 is
- R91 is a branched or straight-chained Cio-Cgoo alkyl or alkenyl group; or R 8 and R9 together are a C 1 -C 4 branched or straight chained alkyl group optionally substituted with one or more amine groups; and further wherein the -N(R 3 i)-R 3 - repeat unit is optionally interrupted in one or more places by a nitrogen-containing heterocyclic cycloalkyl group; and
- R4 and R 5 are each independently selected from (a) hydrogen; (b) a bond connected to R31 in the last distal -N(R 3 i)-R 3 - repeat unit; or (c) -R5-R7, wherein R 6 is C 1 -C 4 branched or straight chained alkylene group, and R 7 is
- R 7 i is a branched or straight-chained Cio-Cgoo alkyl or alkenyl group
- n is an integer between 0 and 10 inclusive
- the groups R 2 ', R 3 ', R 3 i', R 4 ' and R 5 ' are each defined the same as R 2 , R 3 , R 3 i and R4, and R 5 , respectively; and wherein in Formula D, z is 1 or 2, and y is an integer between 1 and 5 inclusive.
- At least one of Ri, R 7 i, and R91 of the compounds shown above comprises polypropylene (PP), which can be atactic polypropylene or isotactic polypropylene.
- the polypropylene can be amorphous, and can include isotactic or syndiotactic crystallizable units.
- the polypropylene includes meso diads constituting from about 30% to about 99.5% of the total diads of the polypropylene.
- at least one of R ls R 71 , and R91 of the compounds above comprises polyethylene (PE).
- At least one of Ri, R 7 i, and R91 of the compounds above comprises poly(ethylene-co-propylene) (EP).
- the mole percentage of the ethylene units and propylene units in the poly(ethylene-co-propylene) can vary.
- the poly(ethylene-co-propylene) can contain about 1 to about 90 mole % of ethylene units and about 99 to about 10 mole % propylene units.
- the poly(ethylene-co-propylene) can contain about 10 to about 90 mole % of ethylene units and about 90 to about 10 mole % propylene units.
- the poly(ethylene- co-propylene) contains about 20 to about 50 mole% of ethylene units.
- At least one of R ls R71, and R91 of the compounds above has a number-averaged molecular weight of from about 300 to about 30,000 g/mol (assuming one olefin unsaturation per chain, as measured by 1H NMR).
- At least one of Ri, R71, and R91 of the additive of the compounds above has a number-averaged molecular weight of from about 500 to 5,000 g/mol.
- the PP or EP included in the Ri, R71 or R91 of the compounds above, individually, has a molecular weight from about 300 to about 30,000 g/mol, or from about 500 to about 5000 g/mol.
- the PP or EP groups have a molecular weight, individually, ranging from about 500 to about 2500 g/mol, or a molecular of from about 500 to about 650 g/mol, or a molecular weight of from about 800 to about 1000 g/mol, or a molecular weight of from about 2000 to about 2500 g/mol.
- At least one of Ri, R71, and R91 comprises poly(higher alpha-olefm) or poly(propylene-co-higher alpha-olefm), the higher alpha-olefm including two or more carbon atoms on each side chain.
- suitable higher alpha- olefms can include, but are not limited to, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1- octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1- hexadecene, 1-octadecene and the like.
- the nitrogen content in the compounds above is about 1 wt% to about 10 wt% based on the total weight of the compound.
- R3 is -CH 2 -CH 2 -, and R31 is hydrogen.
- the -N(R 3 i)-R 3 - repeat unit can be interrupted in one or more places by a 1,4- diethylenediamine.
- U.S. Patent Publication No. 20100170829 provides a detailed description of the compounds and methods of making the compounds.
- the disclosure of U.S. Patent Publication No. 20100170829 is hereby incorporated by reference in its entirety.
- compounds of Formula C such compounds can be obtained by the methods disclosed below, where the vinylidene-terminated polymer base unit is reacted with maleic anhydride without a radical initiator.
- An exemplary protocol for the synthesis of a Formula C intermediate is provided below in Example 1 A, while an exemplary protocol for the condensation of the Formula C intermediate with a polyamine to yield a species of Formula C is disclosed below in Example ID.
- a method for preparing a compound for treating an emulsion of crude hydrocarbon in a hydrocarbon refining process includes:
- R 2 i is a branched or straight-chained Cio-Cgoo alkyl or alkenyl group
- Ri 2 is hydrogen or a C 1 -C 4 branched or straight chained alkyl optionally substituted with one or more amine groups
- R 13 is a C 1 -C 4 branched or straight chained alkylene group
- x is an integer between 1 and 10
- the -N(Ri 2 )-Ri 3 - unit is optionally interrupted in one or more places by a nitrogen-containing heterocyclic cycloalkyl group, and wherein when the x-th -N(Ri 2 )-Ri3- unit along with the terminal nitrogen atom forms a heterocyclic cycloalkyl group, the terminal -NH 2 is replaced by a -NH- group for valency.
- the polymer base unit Rn has a number-averaged molecular weight of 300 to 30,000 g/mol (assuming one olefin
- the polymer base unit Rn comprises polypropylene.
- the polypropylene can be either atactic polypropylene or isotactic polypropylene.
- the polypropylene can be amorphous, and can include isotactic or syndiotactic crystallizable units.
- the polypropylene includes meso diads constituting from about 30% to about 99.5% of the total diads of the polypropylene.
- the polymer base unit Rn can also comprise polyethylene.
- the polymer base unit Rn comprises poly(ethylene-co- propylene).
- the poly(ethylene-co-propylene) can contain from about 1 or 10 mole% to about 90 or 99 mole% of ethylene units and from about 99 or 90 mole% to about 10 or 1 mole% propylene units.
- the poly(ethylene-co-propylene) polymer contains from about 2 or 20 mole% to about 50 mole% ethylene units.
- the PP or EP included in Rn to form Formula I individually has a number-averaged molecular weight ( n ) molecular weight from about 300 to about 30,000 g/mol, or from about 500 to about 5000 g/mol (assuming one olefin unsaturation per chain, as measured by 1H NMR).
- the PP or EP groups have a molecular weight, individually, ranging from about 500 to about 2500 g/mol, or a molecular of from about 500 to about 650 g/mol, or a molecular weight of from about 800 to about 1000 g/mol, or a molecular weight of from about 2000 to about 2500 g/mol.
- the polymer base unit Rn includes polypropylene or poly(ethylene-co-propylene)
- such groups can be prepared, for example, by metallocene- catalyzed polymerization of propylene or a mixture of ethylene and propylene, which are then terminated with a high vinyl group content in the chain end.
- the number-averaged molecular weight ( n ) of the PP or EP can be from about 300 to about 30,000 g/mol, as determined by 1H NMR spectroscopy.
- the vinyl-terminated atactic or isotactic polypropylenes (v-PP) or vinyl-terminated poly(ethylene-co-propylene) (v-EP) suitable for further chemical functionalization can have a molecular weight ( n ) approximately from about 300 to about 30,000 g/mol, and preferably about 500 to 5,000 g/mol.
- the terminal olefin group can be a vinylidene group or an allylic vinyl group (both covered in Formula I). In certain embodiments, the terminal olefin group is an allylic vinyl group.
- the terminal allylic vinyl group rich PP or EP as disclosed in U.S. Patent No. 8,372,930 and U.S Patent Application Publication No. 20090318646, can be used, which are both hereby incorporated by reference in their entirety.
- Some of the vinyl terminated EP or PP according to these co-pending applications contains more than 90 % of allylic terminal vinyl group.
- Rn can comprise propylene and less than 0.5 wt% comonomer, preferably 0 wt% comonomer, wherein the Rn has:
- Mn number average molecular weight
- Mni a number average molecular weight of about 500 to about 20,000 g/mol, as measured by 1 H NMR, assuming one olefin unsaturation per chain (preferably 500 to 15,000, preferably 700 to 10,000, preferably 800 to 8,000 g/mol, preferably 900 to 7,000, preferably 1000 to 6,000, preferably 1000 to 5,000);
- Rn can comprise a propylene copolymer having an Mn of 300 to 30,000 g/mol as measured by 1H NMR and assuming one olefin unsaturation per chain (preferably 400 to 20,000, preferably 500 to 15,000, preferably 600 to 12,000, preferably 800 to 10,000, preferably 900 to 8,000, preferably 900 to 7,000 g/mol), comprising 10 to 90 mol% propylene (preferably 15 to 85 mol%, preferably 20 to 80 mol%, preferably 30 to 75 mol%, preferably 50 to 90 mol%) and 10 to 90 mol% (preferably 85 to 15 mol%, preferably 20 to 80 mol%, preferably 25 to 70 mol%, preferably 10 to 50 mol%) of one or more alpha-olefin comonomers (preferably ethylene, butene, hexene, or octene, or decene, preferably ethylene), wherein the polymer has at least X%
- Rn can have at least 80%) isobutyl chain ends (based upon the sum of isobutyl and n-propyl saturated chain ends), preferably at least 85% isobutyl chain ends, preferably at least 90%> isobutyl chain ends.
- Rn can have an isobutyl chain end to ally lie vinyl group ratio of 0.8: 1 to 1.35:1.0, preferably 0.9: 1 to 1.20: 1.0, preferably 0.9: 1.0 to 1.1 : 1.0.
- Rn can comprise a polypropylene copolymer having more than 90 mol% propylene (preferably 95 to 99 mol%, preferably 98 to 9 mol%) and less than 10 mol% ethylene (preferably 1 to 4 mol%, preferably 1 to 2 mol%), wherein the copolymer has:
- allyl chain ends preferably at least 93% allyl chain ends (preferably at least 95%, preferably at least 97%, preferably at least 98%);
- Mn a number average molecular weight (Mn) of about 400 to about 30,000 g/mol, as measured by 1 H NMR and assuming one olefin unsaturation per chain (preferably 500 to 20,000, preferably 600 to 15,000, preferably 700 to 10,000 g/mol, preferably 800 to 9,000, preferably 900 to 8,000, preferably 1000 to 6,000);
- less than 1400 ppm aluminum (preferably less than 1200 ppm, preferably less than 1000 ppm, preferably less than 500 ppm, preferably less than 100 ppm).
- Rn can comprise a polypropylene copolymer comprising:
- allyl chain ends preferably at least 91%, preferably at least 93%, preferably at least 95%, preferably at least 98%;
- Rn can comprise a polypropylene copolymer comprising: at least 50 (preferably at least 60, preferably 70 to 99.5, preferably 80 to 99, preferably 90 to 98.5) mol% propylene, from 0.1 to 45 (preferably at least 35, preferably 0.5 to 30, preferably 1 to 20, preferably 1.5 to 10) mol% ethylene, and from 0.1 to 5 (preferably 0.5 to 3, preferably 0.5 to 1) mol% C 4 to C 12 olefin (such as butene, hexene or octene, or decene, preferably butene), wherein the polymer has:
- allyl chain ends preferably at least 91%, preferably at least 93%, preferably at least 95%, preferably at least 98%;
- Mn a number average molecular weight (Mn) of about 150 to about 15,000 g/mol, as measured by 1H NMR and assuming one olefin unsaturation per chain (preferably 200 to 12,000, preferably 250 to 10,000, preferably 300 to 10,000, preferably 400 to 9500, preferably 500 to 9,000, preferably 750 to 9,000); and
- Rn can comprise a polypropylene copolymer comprising: at least 50 (preferably at least 60, preferably 70 to 99.5, preferably 80 to 99, preferably 90 to 98.5) mol% propylene, from 0.1 to 45 (preferably at least 35, preferably 0.5 to 30, preferably 1 to 20, preferably 1.5 to 10) mol% ethylene, and from 0.1 to 5 (preferably 0.5 to 3, preferably 0.5 to 1) mol% diene (such as C 4 to C 12 alpha-omega dienes (such as butadiene, hexadiene, octadiene), norbornene, ethylidene norbornene, vinylnorbornene, norbornadiene, and dicyclopentadiene), wherein the polymer has:
- allyl chain ends preferably at least 91%, preferably at least 93%, preferably at least 95%, preferably at least 98%;
- Mn a number average molecular weight (Mn) of about 150 to about 20,000 g/mol, as measured by 1 H NMR and assuming one olefin unsaturation per chain (preferably 200 to 15,000, preferably 250 to 12,000, preferably 300 to 10,000, preferably 400 to 9,500, preferably 500 to 9,000, preferably 750 to 9,000); and
- Rn can comprise poly(higher alpha- olefin) or poly(propylene-co-higher alpha-olefin), the higher alpha-olefin including two or more carbon atoms on each side chain.
- suitable higher alpha-olefms can include, but are not limited to, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1- nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-hexadecene, 1- octadecene and the like.
- Rn includes those vinyl terminated macromonomers disclosed in U.S. Patent Application Publication Nos. 20120245312, 20120245310, 20120245311, 20120245313, and U.S. Provisional Application No. 61/704,604, the disclosure of each of which is incorporated by reference in its entirety herein.
- maleic anhydride can be used for the reaction of converting a polymer base unit Rn having a terminal vinyl functionality to a compound of Formula I.
- the reaction can proceed through a thermal condition (e.g., at temperature of about 150°C to 260°C) without using external radical providers, such as a peroxide initiator. Under this condition, a compound of Formula I can be obtained, along with a polymer having a mono-succinic anhydride terminal group.
- a thermal reaction between Rn and maleic anhydride can be illustrated below in Scheme 1 using a vinyl terminated polypropylene as an example of Rn.
- the above reaction can be carried out without the use of any solvent.
- any inert solvent e.g., paraffinic solvent, naphthenic solvent, aromatic solvent, halogenated solvent, mineral oil, synthetic fluid, etc.
- the reaction can be conducted in an open system under atmospheric pressure by using standard laboratory glassware or in a closed system by using an autoclave (or any sealed vessel suitable for maintaining pressure).
- a catalyst can also be used to
- the vinyl terminated polymer can also be a copolymer of polypropylene, for
- the above reactions can be performed at temperatures between about 150 °C to about 260 °C and between about atmospheric pressure to about 500 psi.
- the reaction can be conducted in an open system under atmospheric pressure by using standard laboratory
- reaction time can vary from minutes to hours depending on the conditions used. The rate of reaction will increase with increased temperature and pressure. At temperatures between about 220-260 °C at elevated pressure, high conversion of the vinyl-terminated polymers can be achieved within about two hours.
- the charge ratio of vinyl-terminated polymers to maleic anhydride in the reactions depicted in Scheme 1 , Scheme 2 and Scheme 3 can vary from about 1 : 1 to about 1 : 10, or preferably from about 1 : 1 to about 1 :6, or preferably from about 1 : 1 to about 1 :4, or preferably from about 1 : 1 to about 1 :3, or preferably from about 1 : 1 to about 1 :2, or preferably from about 1 : 1 to about 1 : 1.5, or preferably from about 1 : 1 to about 1 : 1.2.
- Increasing the charge ratio of maleic anhydride to vinyl-terminated polymer will increase the proportion of di-succinic anhydride product and decrease the proportion of mono- succinic anhydride product. Additionally, at a given temperature, increasing the reaction time will increase the proportion of di-succinic anhydride reaction products relative to mono-succinic anhydride products, provided that sufficient maleic anhydride is present in the reaction system.
- the method of preparing the compound B can include reacting the succinic anhydride-containing polymers obtained above with a polyamine (PAM).
- the reaction can proceed through a condensation mechanism.
- the polyamine can include linear, branched or cyclic isomers of an oligomer of ethyleneamine, or mixtures thereof, wherein each two neighboring nitrogens in the oligomer of ethyleneamine are bridged by one or two ethyleneamine groups.
- the polyamine can be selected from
- the polyamine can comprise a heavy polyamine, such as poly ethyleneamine heavy bottoms available from Dow Chemical as "Heavy Polyamine X" or HPA-X.
- nucleophilic reagents other than polyamines can be used to functionalize the compounds of Formula I.
- These reagents include, for example, monoamines, diamines, amino alcohols, polyetheramines, polyols, polyalkylene glycols, polyalkylene polyamine and the like.
- vinylidene-terminated polymer or copolymer e.g., ethylene-propylene copolymer, and propylene-higher alpha-olefm copolymer
- Rn vinylidene-terminated polymer or copolymer
- the number of polymer chain attached to each polyamine molecule can vary from one to two to three or more.
- both primary and secondary amino groups on the polyamine can participate in the reaction with the anhydride-functionalized polymer.
- Other commercially available lower or higher polyamines with linear, branched, cyclic or heterocyclic structures can also be used. It is well-known and understood by those skilled in the art that these polyamines can be mixtures of compounds comprised of molecules with a distribution of chain lengths, different level and type of amine (primary, secondary, and tertiary) functional groups, and varying degree of linear, branched and cyclic structures. For example, possible isomers for
- tetraethylenepentamine include the following:
- a method for preparing a compound according to Formula D for treating an emulsion of crude hydrocarbon in a hydrocarbon refining process includes: (a) reacting a polymer base unit Rn, which is a branched or straight-chained Cio-Cgoo alkyl or alkenyl group having a vinyl terminal group, with maleic anhydride in the presence of a radical initiator to obtain a olymer represented by Formula II below:
- R 2 i is a branched or straight-chained Ci 0 -C 8 oo alkyl or alkenyl group, z is 1 or 2, and y is an integer between 1 and 5 inclusive;
- Ri 2 is hydrogen or a C 1 -C 4 branched or straight chained alkyl optionally substituted with one or more amine groups
- R 13 is a C 1 -C 4 branched or straight chained alkylene group
- x is an integer between 1 and 10
- the -N(Ri 2 )-Ri 3 - unit is optionally interrupted in one or more places by a nitrogen-containing heterocyclic cycloalkyl group, and wherein when the x-th -N(Ri 2 )-Ri 3 - unit along with the terminal nitrogen atom forms a heterocyclic cycloalkyl group, the terminal -NH 2 is replaced by a - NH- group for valency.
- the polymer base unit Rn has a number-averaged molecular weight of 300 to 30,000 g/mol (assuming one olefin
- the polymer base unit Rn comprises polypropylene.
- the polypropylene can be either atactic polypropylene or isotactic polypropylene.
- the polypropylene can be amorphous, and can include isotactic or syndiotactic crystallizable units.
- the polypropylene includes meso diads constituting from about 30% to about 99.5% of the total diads of the polypropylene.
- the polymer base unit Rn can also comprise polyethylene.
- the polymer base unit Rn comprises poly(ethylene-co- propylene).
- the poly(ethylene-co-propylene) can contain from about 1 or 10 mole% to about 90 or 99 mole% of ethylene units and from about 99 or 90 mole% to about 10 or 1 mole% propylene units.
- the poly(ethylene-co-propylene) polymer contains from about 2 or 20 mole% to about 50 mole% ethylene units.
- the PP or EP included in the Rn to form Formula II individually has a number-averaged molecular weight ( n ) from about 300 to about 30,000 g/mol, or from about 500 to about 5000 g/mol (assuming one olefin unsaturation per chain, as measured by 1H NMR).
- the PP or EP groups have a molecular weight, individually, ranging from about 500 to about 2500 g/mol, or a molecular of from about 500 to about 650 g/mol, or a molecular weight of from about 800 to about 1000 g/mol, or a molecular weight of from about 2000 to about 2500 g/mol.
- polystyrene resin examples include polypropylene or poly(ethylene-co-propylene)
- such groups can be prepared, for example, by metallocene- catalyzed polymerization of propylene or a mixture of ethylene and propylene, which are then terminated with a high vinyl group content in the chain end.
- the number-averaged molecular weight ( n ) of the PP or EP can be from about 300 to about 30,000 g/mol, as determined by 1H NMR spectroscopy.
- polypropylenes (v-PP) or vinyl-terminated poly(ethylene-co-propylene) (v-EP) suitable for further chemical functionalization can have a molecular weight ( n ) approximately from about 300 to about 30,000 g/mol, and preferably about 500 to 5,000 g/mol.
- the terminal olefin group can be a vinylidene group or an allylic vinyl group. In certain embodiments, the terminal olefin group is an allylic vinyl group.
- the terminal allylic vinyl group rich PP or EP as disclosed in U.S. Patent No. 8,372,930 and co-pending application, U.S. Patent Application Publication No. 20090318646, can be used, each of which is hereby incorporated by reference in its entirety.
- Rn can comprise propylene and less than 0.5 wt% comonomer, preferably 0 wt% comonomer, wherein the Rn has:
- Mn number average molecular weight
- Mni a number average molecular weight of about 500 to about 20,000 g/mol, as measured by 1H NMR, assuming one olefin unsaturation per chain (preferably 500 to 15,000, preferably 700 to 10,000, preferably 800 to 8,000 g/mol, preferably 900 to 7,000, preferably 1000 to 6,000, preferably 1000 to 5,000);
- Rn can comprise a propylene copolymer having an Mn of 300 to 30,000 g/mol as measured by 1H NMR and assuming one olefin unsaturation per chain (preferably 400 to 20,000, preferably 500 to 15,000, preferably 600 to 12,000, preferably 800 to 10,000, preferably 900 to 8,000, preferably 900 to 7,000 g/mol), comprising 10 to 90 mol%> propylene (preferably 15 to 85 mol%>, preferably 20 to 80 mol%, preferably 30 to 75 mol%, preferably 50 to 90 mol%) and 10 to 90 mol% (preferably 85 to 15 mol%>, preferably 20 to 80 mol%>, preferably 25 to 70 mol%>, preferably 10 to 50 mol%) of one or more alpha-olefin comonomers (preferably ethylene, butene, hexene, or octene, or decene, preferably ethylene), wherein the polymer has
- Rn can have at least 80%) isobutyl chain ends (based upon the sum of isobutyl and n-propyl saturated chain ends), preferably at least 85%> isobutyl chain ends, preferably at least 90%> isobutyl chain ends.
- Rn can have an isobutyl chain end to ally lie vinyl group ratio of 0.8: 1 to 1.35:1.0, preferably 0.9: 1 to 1.20: 1.0, preferably 0.9: 1.0 to 1.1 : 1.0.
- Rn can comprise a polypropylene copolymer having more than 90 mol% propylene (preferably 95 to 99 mol%, preferably 98 to 9 mol%) and less than 10 mol% ethylene (preferably 1 to 4 mol%, preferably 1 to 2 mol%), wherein the copolymer has:
- allyl chain ends preferably at least 93% allyl chain ends (preferably at least 95%, preferably at least 97%, preferably at least 98%);
- Mn a number average molecular weight (Mn) of about 400 to about 30,000 g/mol, as measured by 1H NMR and assuming one olefin unsaturation per chain (preferably 500 to 20,000, preferably 600 to 15,000, preferably 700 to 10,000 g/mol, preferably 800 to 9,000, preferably 900 to 8,000, preferably 1000 to 6,000);
- less than 1400 ppm aluminum (preferably less than 1200 ppm, preferably less than 1000 ppm, preferably less than 500 ppm, preferably less than 100 ppm).
- Rn can comprise a polypropylene copolymer comprising:
- allyl chain ends preferably at least 91%, preferably at least 93%, preferably at least 95%, preferably at least 98%;
- Rn can comprise a polypropylene copolymer comprising: at least 50 (preferably at least 60, preferably 70 to 99.5, preferably 80 to 99, preferably 90 to 98.5) mol% propylene, from 0.1 to 45 (preferably at least 35, preferably 0.5 to 30, preferably 1 to 20, preferably 1.5 to 10) mol% ethylene, and from 0.1 to 5 (preferably 0.5 to 3, preferably 0.5 to 1) mol% C 4 to C 12 olefin (such as butene, hexene or octene, or decene, preferably butene), wherein the polymer has:
- allyl chain ends preferably at least 91%, preferably at least 93%, preferably at least 95%, preferably at least 98%;
- Mn a number average molecular weight (Mn) of about 150 to about 15,000 g/mol, as measured by 1H NMR and assuming one olefin unsaturation per chain (preferably 200 to 12,000, preferably 250 to 10,000, preferably 300 to 10,000, preferably 400 to 9500, preferably 500 to 9,000, preferably 750 to 9,000); and
- Rn can comprise a polypropylene copolymer comprising: at least 50 (preferably at least 60, preferably 70 to 99.5, preferably 80 to 99, preferably 90 to 98.5) mol% propylene, from 0.1 to 45 (preferably at least 35, preferably 0.5 to 30, preferably 1 to 20, preferably 1.5 to 10) mol% ethylene, and from 0.1 to 5 (preferably 0.5 to 3, preferably 0.5 to 1) mol% diene (such as C 4 to C 12 alpha-omega dienes (such as butadiene, hexadiene, octadiene), norbornene, ethylidene norbornene, vinylnorbornene, norbornadiene, and dicyclopentadiene), wherein the polymer has:
- allyl chain ends preferably at least 91%, preferably at least 93%, preferably at least 95%, preferably at least 98%;
- Mn a number average molecular weight (Mn) of about 150 to about 20,000 g/mol, as measured by 1 H NMR and assuming one olefin unsaturation per chain (preferably 200 to 15,000, preferably 250 to 12,000, preferably 300 to 10,000, preferably 400 to 9,500, preferably 500 to 9,000, preferably 750 to 9,000); and
- Rn can comprise poly(higher alpha- olefin) or poly(propylene-co-higher alpha-olefin), the higher alpha-olefin including two or more carbon atoms on each side chain.
- suitable higher alpha-olefms can include, but are not limited to, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1- nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-hexadecene, 1- octadecene and the like.
- Rn includes those vinyl terminated macromonomers disclosed in U.S. Patent Application Publication Nos. 20120245312, 20120245310, 20120245311, 20120245313, and U.S. Provisional Application No. 61/704,604, the disclosure of each of which is incorporated by reference in its entirety herein.
- maleic anhydride can be used for the reaction of converting a polymer base unit Rn having a terminal vinyl functionality to a compound of Formula II.
- the reaction between Rn and maleic anhydride can be initiated by a radical initiator. The reaction under this condition can result in
- the vinyl-terminated polymer and maleic anhydride can be mixed either neat or in an inert solvent (e.g., paraffmic solvent, naphthenic solvent, aromatic solvent, halogenated solvent, mineral oil, synthetic fluid, etc.) with appropriate boiling point or boiling point range.
- an inert solvent e.g., paraffmic solvent, naphthenic solvent, aromatic solvent, halogenated solvent, mineral oil, synthetic fluid, etc.
- the reaction can be conducted in an open system under atmospheric pressure by using standard laboratory glassware or in a closed system by using an autoclave (or any sealed vessel suitable for holding the pressure).
- the temperature can vary from 80 to 180
- Reactant charge ratio of vinyl-terminated polymer to maleic anhydride can vary from about 1 : 1 to about 1 :4, or from about 1 : 1 to about 1 :3, or from about 1 : 1 to about 1 :2, or from about 1 : 1 to about 1 : 1.5, or from about 1 : 1 to about 1 : 1.2.
- Suitable radical initiators include, but not limited to, organic peroxides such as di-tert-butyl peroxide, dicumyl peroxide, lauroyl peroxide, benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxybenzoate (peroxy ester), tert-butyl peracetate (peroxy ester), 2,2'-azobisisobutyronitrile (AIBN), 1 , -azobis(cyclohexanecarbonitrile) or similar diazo compounds.
- organic peroxides such as di-tert-butyl peroxide, dicumyl peroxide, lauroyl peroxide, benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxybenzoate (peroxy ester), tert-butyl peracetate (peroxy ester), 2,2'-azo
- the radical initiator can be introduced in portions over a convenient period of time, if desired for controlling reaction rate, to the mixture of vinyl-terminated polymer and maleic anhydride at a suitable temperature (e.g., from about 120 to 165 °C for di-tert-butyl peroxide) needed for thermal decomposition of the radical initiator to generate radical species at a rate suitable for the reaction.
- a suitable temperature e.g., from about 120 to 165 °C for di-tert-butyl peroxide
- the method of preparing the compounds can include reacting the succinic anhydride-containing polymers obtained above with a polyamine.
- the reaction can proceed through a condensation mechanism.
- the polyamine can include linear, branched or cyclic isomers of an oligomer of ethyleneamine, or mixtures thereof, wherein each two neighboring nitrogens in the oligomer of ethyleneamine are bridged by one or two ethyleneamine groups.
- the polyamine can be selected from
- the polyamine can comprise a heavy polyamine, such as poly ethyleneamine heavy bottoms available from Dow Chemical as "Heavy Polyamine X" or HPA-X.
- nucleophilic reagents other than polyamines can be used to functionalize the compounds of Formula II.
- These reagents include, for example, monoamines, diamines, amino alcohols, polyetheramines, polyols, polyalkylene glycols, polyalkylene poly amine and the like.
- vinylidene-terminated polymer or copolymer e.g., ethylene-propylene copolymer, and propylene-higher alpha-olefm copolymer
- Rn vinylidene-terminated polymer or copolymer
- the number of polymer chain attached to each polyamine molecule can vary from one to two to three or more.
- both primary and secondary amino groups on the polyamine can participate in the reaction with the anhydride-functionalized polymer.
- Other commercially available lower or higher polyamines with linear, branched, cyclic or heterocyclic structures can also be used. It is well-known and understood by those skilled in the art that these polyamines can be mixtures of compounds comprised of molecules with a distribution of chain lengths, different level and type of amine (primary, secondary, and tertiary) functional groups, and varying degree of linear, branched and cyclic structures. For example, possible isomers for
- tetraethylenepentamine include the following:
- a method for demulsifying a crude hydrocarbon emulsion in a hydrocarbon refining process comprises providing an emulsion of a crude hydrocarbon, and adding an additive to the emulsion to obtain a treated hydrocarbon, the additive being represented by one or more of Formula A, B, C, and D above.
- Another aspect of the disclosed subject matter provides a system for refining hydrocarbons that includes at least one crude hydrocarbon refinery component, in which the crude hydrocarbon refinery component includes a compound selected from any one of the compounds described herein.
- the crude hydrocarbon refining component can be selected from a heat exchanger, a furnace, a crude preheater, a coker preheater, a FCC slurry bottom, a debutanizer exchanger, a debutanizer tower, a feed/effluent exchanger, a furnace air preheater, a flare compressor component, a steam cracker, a steam reformer, a distillation column, a fractionation column, a scrubber, a reactor, a liquid-jacketed tank, a pipestill, a coker, and a visbreaker.
- the crude hydrocarbon refining component can be a desalter. Such methods and systems are described in greater details in the following sections and examples.
- the additives of the disclosed subject matter are generally soluble in a typical hydrocarbon refinery stream and can thus be added directly to the process stream, alone or in combination with other additives that promote demulsification or improve some other process parameter.
- the additives can be introduced, for example, upstream from the particular crude hydrocarbon refinery component(s) (e.g., a desalter) in which it is desired to promote demulsification (e.g. separation of water and crude).
- the additive can be added to the crude oil prior to being introduced to the refining process, or at the very beginning of the refining process.
- one aspect of the disclosed subject matter provides a method of demulsifying, in particular, crude hydrocarbon emulsions that includes adding at least one additive of the disclosed subject matter to a process stream after mixture of the stream with water to extract salts and foulants.
- a method to promote demulsification comprising adding any one of the above-mentioned additives or compositions to a crude hydrocarbon refinery component that is in fluid communication with a process stream that contains a crude hydrocarbon emulsion.
- the total amount of additive to be added to the process stream can be determined by a person of ordinary skill in the art. In one embodiment, up to about 1000 wppm of additive is added to the process stream.
- the additive can be added such that its concentration, upon addition, is about 50 ppm, 250 ppm or 500 ppm. More or less additive can be added depending on, for example, the degree of demulsification desired in view of the cost of the additive.
- the additives or compositions of the disclosed subject matter can be added in a solid (e.g. powder or granules) or liquid form directly to the process stream. Any suitable technique can be used for adding the additive to the process stream, as known by a person of ordinary skill in the art in view of the process to which it is employed. As a non-limiting example, the additives or compositions can be introduced via injection that allows for sufficient mixing of the additive and the process stream.
- Figure 1 demonstrates possible additive injection points within the refinery crude pre-heat train for the additives of the disclosed subject matter, wherein the numbered circles represent heat exchangers.
- the additives can be introduced in crude storage tanks and at several locations in the preheat train. This includes at the crude charge pump (at the very beginning of the crude pre-heat train), and/or before the desalter or dehydrator. It is contemplated that the additive may be added at any point prior to the crude oil entering the desalter unit.
- the additives or compositions of the disclosed subject matter can be added in a solid (e.g. powder or granules) or liquid form directly to the process stream.
- the additives or compositions can be added alone, or combined with other components to form a composition for demulsification.
- Any suitable technique can be used for adding the additive to the process stream, as known by a person of ordinary skill in the art in view of the process to which it is employed.
- compositions can be introduced via injection that allows for sufficient mixing of the additive and the process stream.
- Example 1A Maleation of vinylidene-terminated polyisobutylene (PIB) with maleic anhydride
- N 2 inlet and an N 2 outlet was added highly reactive polyisobutylene (BASF Glissopal 2300, 85 g) followed by maleic anhydride (15.65 g, 159.6 mmol) at room temperature.
- the mixture was stirred and flushed three times with nitrogen at room temperature and pressurized to 80 psi.
- the mixture was heated to 250 °C for 2 hours and allowed to cool to room temperature. The pressure was released slowly and the autoclave was opened.
- the mixture was diluted with hexanes, filtered under house vacuum and the filtrate was concentrated on a rotary evaporator.
- the mixture was heated at 95 °C under high vacuum to afford a viscous light brown oily product (90.66 g).
- Elemental analyses for this PIB-SA material found C: 82.44%, H: 13.25%.
- the oxygen content of this material is estimated to be about 4.31 wt% by difference.
- the anhydride content of this polymer material is estimated to be about 0.898 mmol/g. Based on the molecular weight of polymer starting material, there is an average of 2.10 succinic anhydride functionality per polymer chain.
- Example IB Maleation of vinyl-terminated polypropylene (vt-PP) with maleic anhydride
- Example 1C Maleation of vinyl-terminated propylene/l-hexene copolymer with maleic anhydride
- N 2 outlet was added vinyl-terminated atactic polypropylene (GPC M w 5646, M n 1474, 1H NMR Mn 1190.19 g/mol, 75.00 g, 63.02 mmol) followed by maleic anhydride (15.45 g, 157.56 mmol) at room temperature.
- the mixture was flushed with nitrogen for 10 min at room temperature and the mixture was heated to 190 °C (oil bath) for 63.5 hours under a nitrogen atmosphere.
- Additional maleic anhydride (3.10 g, 31.61 mmol) was added to the mixture that had been cooled to about 120 °C and heating was continued at 190 °C (oil bath) for an additional 17 hours under a nitrogen atmosphere.
- N 2 outlet was added vinyl-terminated propylene/l-hexene copolymer (GPC M w 1259, M n 889, 1H NMR Mn 846.53 g/mol, 150 g, 177.19 mmol) followed by maleic anhydride (43.44 g, 442.99 mmol) at room temperature.
- the mixture was flushed with nitrogen for 10 min at room temperature and the mixture was heated to 190 °C (oil bath) for 38.5 hours under a nitrogen atmosphere.
- the mixture was cooled to room temperature, diluted with hexanes, filtered and concentrated on a rotary evaporator.
- N 2 outlet was added vinyl-terminated propylene/l-butene copolymer (GPC M w 2197, M n 1030, 1H NMR Mn 1062.16 g/mol, 50 g, 47.07 mmol) followed by maleic anhydride (9.23 g, 94.13 mmol) at room temperature.
- the mixture was flushed with nitrogen for 10 min at room temperature and the mixture was heated to 190 °C (oil bath) for 84.5 hours under a nitrogen atmosphere.
- the mixture was cooled to room temperature, diluted with hexanes, filtered and concentrated on a rotary evaporator.
- DMA4 tetraethylenepentamine
- Example IP Condensation of propylene/l-butene succinic anhydride (C 3 C 4 -SA) with tetraethylenepentamine (TEPA)
- Example 1Q Copolymerization of vinyl-terminated atactic polypropylene with maleic anhydride
- a mixture of vinyl-terminated atactic polypropylene (NB# 25136-002-001,
- the mixture was cooled to room temperature and excess solvent and volatile material were removed on a rotary evaporator.
- the crude product was further purified by heating at 95 °C under high vacuum to afford a light yellow viscous material (17.26 g).
- the conversion of polypropylene starting material was about 81% according to 1H NMR spectroscopy.
- the molecular weight of the material was determined to be M w 4247, M n 1977 (by GPC). Elemental analyses for this PP-MA copolymer material found C: 81.01%, H: 12.56%.
- the oxygen content of this material is estimated to be about 6.43 wt% by difference.
- the anhydride content of this polymer material is estimated to be about 1.340 mmol/g.
- Example 1R Copolymerization of vinyl-terminated atactic polypropylene with maleic anhydride
- the conversion of polypropylene starting material was about 83% according to 1H NMR spectroscopy.
- the molecular weight of the material was determined as M w 6552, M n 2539 (by GPC). Elemental analyses for this PP-MA copolymer material found C: 82.89%, H: 13.10%.
- the oxygen content of this material is estimated to be about 4.01 wt% by difference.
- the anhydride content of this polymer material is estimated to be about 0.835 mmol/g.
- Example IS Copolymerization of vinyl-terminated propylene/l-hexene copolymer with maleic anhydride
- the mixture was cooled to room temperature and excess solvent and volatile material were removed on a rotary evaporator.
- the crude product was further purified by heating at 95 °C under high vacuum to afford a light yellow viscous material (34.22 g).
- the conversion of propylene/l-hexene copolymer starting material was about 87% according to 1H NMR spectroscopy. Elemental analyses for this C 3 C 6 -MA copolymer material found C: 81.79%, H: 13.02%.
- the oxygen content of this material is estimated to be about 5.19 wt% by difference.
- the anhydride content of this polymer material is estimated to be about 1.081 mmol/g.
- Example IT Functionalization of polypropylene maleic anhydride copolymer with tetraethylenepentamine
- Example 1U Functionalization of polypropylene-maleic anhydride copolymer with tetraethylenepentamine
- MA) copolymer (8.00 g, from Example IS, 8.65 mmol anhydride) and xylenes (55 ml) was stirred at room temperature under a nitrogen atmosphere and a solution of triethylenetetramine (0.903 g, 6.18 mmol) in xylenes (5 ml) was slowly added.
- the resulting mixture was heated in an oil bath at 165 °C for 24 hours under a nitrogen atmosphere and an azeotropic mixture of xylenes and water was collected in a Dean-Stark trap.
- the light brown mixture was cooled to room temperature and excess xylenes removed on a rotary evaporator.
- copolymer additive found C: 80.39%, H: 12.78%, N: 3.62%.
- N 2 outlet was added vinyl-terminated atactic polypropylene (GPC M w 5087, M n 2449, 1H NMR Mn 2009.73 g/mol, 190.00 g, 94.54 mmol) followed by maleic anhydride (27.81 g, 283.60 mmol) at room temperature.
- the mixture was flushed with nitrogen for 10 min at room temperature and the mixture was heated to 190 °C (oil bath) for 65 hours under a nitrogen atmosphere.
- the mixture was cooled to room temperature, diluted with hexanes, filtered and concentrated on a rotary evaporator.
- N 2 outlet was added vinyl-terminated atactic polypropylene (GPC M w 4694, M n 2215, 1H NMR Mn 1880.45 g/mol, 150.00 g, 79.77 mmol) followed by maleic anhydride (31.28 g, 319.0 mmol) at room temperature.
- the mixture was flushed with nitrogen for 10 min at room temperature and the mixture was heated to 190 °C (oil bath) for 53 hours under a nitrogen atmosphere.
- the mixture was cooled to room temperature, diluted with hexanes, filtered and concentrated on a rotary evaporator.
- Example 1Y Condensation of polypropylene succinic anhydride with tetraethylenepentamine (DMA2)
- Example 1Z Condensation of polypropylene succinic anhydride with tetraethylenepentamine (DMA3)
- polyisobutylene succinimide dispersants were obtained from commercial suppliers (Infineum, Lubrizol, Chevron Oronite, Afton Chemical, BASF, etc).
- polyisobutylene-based polyamine succinimide dispersants were prepared by using commercially available highly reactive polyisobutylenes (HR-PIB) from BASF and from Texas Petrochemcials (TPC) as exemplified below.
- HR-PIB highly reactive polyisobutylenes
- TPC Texas Petrochemcials
- the presently disclosed subject matter can include one or more of the following embodiments.
- Embodiment 1 A method for treating an emulsion of a hydrocarbon, comprising (i) providing an emulsion of a crude hydrocarbon; (ii) adding an additive to the emulsion to obtain a treated hydrocarbon, the additive being represented by one of Formula A, B, C, and D below:
- R 2 is a C1-C4 branched or straight chained alkylene group;
- R3 is a C1-C4 branched or straight chained alkylene group;
- R31 is hydrogen or -R8-R , wherein R 8 is C1-C4 branched or straight chained alkylene group, and R9 is
- R91 is a branched or straight-chained Cio-Cgoo alkyl or alkenyl group; or R 8 and R9 together are a C1-C4 branched or straight chained alkyl group optionally substituted with one or more amine groups; and further wherein the -N(R 3 i)-R 3 - repeat unit is optionally interrupted in one or more places by a nitrogen-containing heterocyclic cycloalkyl group; and R 4 and R 5 are each independently selected from (a) hydrogen; (b) a bond connected to R 3 i in the last distal -N(R 3 i)-R 3 - repeat unit; or (c) -R 6 -R 7 , wherein R ⁇ 5 is C1-C4 branched or straight chained alkylene group, and R 7 is
- R 7 i is a branched or straight-chained Cio-Csoo alkyl or alkenyl group; wherein in Formula B, n is an integer between 0 and 10 inclusive, and the groups R 2 ', R 3 ', R 3 i ' , R4' and R 5 ' are each defined the same as R 2 , R 3 , R 3 i and R 4 , and R 5 , respectively; wherein in Formula D, z is 1 or 2, and y is an integer between 1 and 5 inclusive.
- Embodiment 2 The method of embodiment 1, wherein at least one of Ri,
- R 7 i, and R91 comprises polypropylene.
- Embodiment 3 The method of embodiment 2, wherein the polypropylene is atactic polypropylene, isotactic polypropylene, or syndiotactic polypropylene.
- Embodiment 4 The method of embodiment 2, wherein the polypropylene is amorphous.
- Embodiment 5 The method of embodiment 2, wherein the polypropylene includes isotactic or syndiotactic crystallizable units.
- Embodiment 6 The method of embodiment 2, wherein the polypropylene includes meso diads constituting from about 30% to about 99.5% of the total diads of the polypropylene.
- Embodiment 7 The method of embodiment 2, wherein at least one of
- Ri, R71, and R91 has a number-averaged molecular weight of from about 300 to about 30000 g/mol.
- Embodiment 8 The method of embodiment 2, wherein at least one of
- Ri, R71, and R91 has a number-averaged molecular weight of from about 500 to about 5000 g/mol.
- Embodiment 9 The method of embodiment 1 , wherein at least one of
- Ri, R71, and R91 comprises polyethylene.
- Embodiment 10 The method of embodiment 1 , wherein at least one of
- Ri, R71, and R91 comprises poly(ethylene-co-propylene).
- Embodiment 1 1 The method of embodiment 10, wherein at least one of
- Ri, R71, and R91 comprises from about 1 mole % to about 90 mole % of ethylene units and from about 99 mole % to about 10 mole% propylene units.
- Embodiment 12 The method of embodiment 1 1 , wherein at least one of
- Ri, R71, and R91 comprises from about 10 mole % to about 50 mole % of ethylene units.
- Embodiment 13 The method of embodiment 1 , wherein at least one of
- Ri, R71, and R91 comprises poly(higher alpha-olefm), the higher alpha-olefm including two or more carbon atoms on each side chain.
- Embodiment 14 The method of embodiment 1 , wherein at least one of
- Ri, R71, and R91 comprises poly(propylene-co-higher alpha-olefm), the higher alpha-olefm including two or more carbon atoms on each side chain.
- Embodiment 15 The method of any one of the previous embodiments, wherein the nitrogen content in the compound is about 1 wt% to about 10 wt% based on the total weight of the compound.
- Embodiment 16 The method of any one of the previous embodiments, wherein R 3 is -CH 2 -CH 2 -, and R 3 i is hydrogen.
- Embodiment 17 The method of embodiment 16, wherein the -N(R 3 i)-
- R 3 - repeat unit is interrupted in one or more places by a 1,4-diethylenediamine.
- Embodiment 18 The method of any one of the previous embodiments, wherein the treated hydrocarbon is in a hydrocarbon phase as a result of demulsification of the emulsion.
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Abstract
A method for treating an emulsion of a hydrocarbon is disclosed. The method includes providing an emulsion of a crude hydrocarbon, and adding an additive to the emulsion to obtain a treated hydrocarbon.
Description
FUNC TIO ALIZED POLYMERS CONTAINING POLYAMINE SUCCINIMIDE FOR DEMULSIFICATION IN HYDROCARBON REFINING PROCESSES
TECHNICAL FIELD
[0001] The disclosed subject matter relates to additives to demulsify a hydrocarbon emulsion and methods and systems using the same.
BACKGROUND
[0002] Desalting is one of the first steps in crude refining. This is done to remove salts and particulates to reduce corrosion, fouling and catalyst poisoning. In a typical desalting process, fresh water is mixed with oil to produce a water-in-oil emulsion which in turn extracts salt and brine and some particulates from oil. The salty emulsion is then sent to a desalter unit where the application of an electric field forces water droplets to coalesce. Large electrocoalesced water droplets settle under gravity and separate from the desalted oil. Electrocoalescence (i.e. coalescence under electric field) is also used to dehydrate crude at or near production sites to remove water before sending to the refinery.
[0003] To aid the desalting process, chemical additives known as demulsifiers are added to crudes and/or emulsions. The material properties of these demulsifiers allow them to remain in the oil phase of an emulsion. These additives reduce the emulsion stability, causing an enhancement in water separation, desalting and electrocoalescence and thus emulsion resolutions.
SUMMARY
[0004] The disclosed subject matter provides demulsifying chemical additives for treating a hydrocarbon emulsion. These additives can stay in the oil phase, and therefore can be added to a crude oil or emulsion as demulsifiers to enhance the desalting process.
[0005] In accordance with one aspect of the disclosed subject matter, a method for treating an emulsion of a hydrocarbon is provided. The method includes: (i) providing an emulsion of a crude hydrocarbon, and (ii) adding an additive to the emulsion to obtain a treated hydrocarbon, the additive being represented by one of Formula A, B, C, and D below:
wherein in each of the Formula A, B, C, and D above:
m is an integer between 0 and 10 inclusive;
Ri is a branched or straight-chained Cio-Cgoo alkyl or alkenyl group;
R2 is a C1-C4 branched or straight chained alkylene group;
R3 is a C1-C4 branched or straight chained alkylene group;
R31 is hydrogen or -Rg-Rg, wherein Rg is C1-C4 branched or straight chained alkylene group, and R9 is
wherein R91 is a branched or straight-chained Cio-Cgoo alkyl or alkenyl group; or Rg and R9 together are a C1-C4 branched or straight chained alkyl group optionally substituted with one or more amine groups; and further wherein the -N(R3i)-R3- repeat unit is optionally interrupted in one or more places by a nitrogen-containing heterocyclic cycloalkyl group; and
R4 and R5 are each independently selected from (a) hydrogen; (b) a bond connected to R31 in the last distal -N(R3i)-R3- repeat unit; or (c) -R6-R7, wherein R6 is C1-C4 branched or straight chained alkylene group, and R7 is
wherein in Formula B, n is an integer between 0 and 10 inclusive, and the groups R2' , R3 ', R3i ' , R4' and R5 ' are each defined the same as R2, R3, R3i and R4, and R5, respectively;
wherein in Formula D, z is 1 or 2, and y is an integer between 1 and 5 inclusive.
[0006] According to another aspect of the disclosed subject matter, a compound of Formula B as noted above is provided.
[0007] According to another aspect of the disclosed subject matter, a method for preparing a compound for treating an emulsion of crude hydrocarbon in a hydrocarbon refining process is provided. The method includes:
(a) reacting a polymer base unit Rn, which is a branched or straight-chained Cio-Cgoo alkyl or alkenyl group having a vinyl terminal group, with maleic anhydride to obtain a polymer represented by Formula I below:
(b) reacting the polymer obtained in a) with a polyamine represented by
wherein Ri2 is hydrogen or a C1-C4 branched or straight chained alkyl optionally substituted with one or more amine groups, R13 is a C1-C4 branched or straight chained alkylene group, and x is an integer between 1 and 10, and further wherein the -N(Ri2)-Ri3- unit is optionally interrupted in one or more places by a nitrogen-containing heterocyclic cycloalkyl group, and wherein when the x-th -N(Ri2)-Ri3- unit along with the terminal nitrogen atom forms a heterocyclic cycloalkyl group, the terminal -NH2 is replaced by a -NH- group for valency.
[0008] According to a further aspect of the disclosed subject matter, a compound prepared by the above method is provided.
[0009] According to another aspect of the disclosed subject matter, a compound of Formula D as noted above is provided.
[0010] In a further aspect, a method for preparing a compound of Formula D for treating an emulsion of crude hydrocarbon in a hydrocarbon refining process is provided. The method includes:
(a) reacting a polymer base unit Rn, which is a branched or straight-chained Cio-Cgoo alkyl or alkenyl group having a vinyl terminal group, with maleic anhydride to obtain a polymer represented b Formula II below:
(II)
wherein R2i is a branched or straight-chained Cio-Cgoo alkyl or alkenyl group, z is 1 or 2, and y is an integer between 1 and 5 inclusive;
(b) reacting the polymer obtained in a) with a polyamine represented by
wherein Ri2 is hydrogen or a C1-C4 branched or straight chained alkyl optionally substituted with one or more amine groups, R 3 is a C1-C4 branched or straight chained alkylene group, and x is an integer between 1 and 10, and further wherein the -N(Ri2)-Ri3- unit is optionally interrupted in one or more places by a nitrogen-containing heterocyclic cycloalkyl group, and wherein when the x-th -N(Ri2)-Ri3- unit along with the terminal nitrogen atom forms a heterocyclic cycloalkyl group, the terminal -NH2 is replaced by a -NH- group for valency.
[0011] In a further aspect, a compound prepared by the above method is provided.
[0012] In addition, the disclosed subject matter provides compositions comprising such additives, and systems for refining hydrocarbons containing such additives and
compositions.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] The disclosed subject matter will now be described in conjunction with the accompanying drawings in which:
[0014] FIG. 1 is a representation of an oil refinery crude pre -heat train, annotated to show non-limiting injection points for the additives of the disclosed subject matter.
|0015| FIG. 2 A is a plot illustrating the effects of an additive of the present application in treating an emulsion; FIG. 2B show images of an emulsion as treated by the additive as compared with a control experiment.
[0016] FIG. 3 is a plot illustrating the effects of various additives of the disclosed subject matter in treating an emulsion.
DETAILED DESCRIPTION
Definitions
[0017] The following definitions are provided for purpose of illustration and not limitation.
[0018] As used herein, the term "demulsifier" refers to a chemical suitable for addition crude oil to enhance the phase separation (for example, water separation) of a crude
hydrocarbon emulsion in a refinery process, such as in a desalter or dehydrator.
[0019] As used herein, the term "alkyl" refers to a monovalent hydrocarbon group containing no double or triple bonds and arranged in a branched or straight chain.
[0020] As used herein, the term "alkylene" refers to a divalent hydrocarbon group containing no double or triple bonds and arranged in a branched or straight chain.
[0021] As used herein, the term "alkenyl" refers to a monovalent hydrocarbon group containing one or more double bonds and arranged in a branched or straight chain.
[0022] As used herein, a "hydrocarbyl" group refers to any univalent radical that is derived from a hydrocarbon, including univalent alkyl, aryl and cycloalkyl groups.
[0023] As used herein, the term "crude hydrocarbon refinery component" generally refers to an apparatus or instrumentality of a process to refine crude hydrocarbons, such as an oil refinery process, which is, or can be, susceptible to fouling. Crude hydrocarbon refinery components include, but are not limited to, heat transfer components such as a heat exchanger, a furnace, a crude preheater, a coker preheater, or any other heaters, a FCC slurry bottom, a debutanizer exchanger/tower, other feed/effluent exchangers and furnace air preheaters in refinery facilities, flare compressor components in refinery facilities and steam cracker/reformer tubes in petrochemical facilities. Crude hydrocarbon refinery components can also include other instrumentalities in which heat transfer can take place, such as a fractionation or distillation column, a scrubber, a reactor, a liquid-jacketed tank, a pipestill, a coker and a visbreaker. It is understood that "crude hydrocarbon refinery components," as used herein, encompasses tubes, piping, baffles and other process transport mechanisms that are internal to, at least partially constitute, and/or are in direct fluid communication with, any one of the above-mentioned crude hydrocarbon refinery components.
[0024] As used herein, reference to a group being a particular polymer (e.g., polypropylene or poly(ethylene-co-propylene) encompasses polymers that contain primarily the respective monomer along with negligible amounts of other substitutions and/or interruptions along the polymer chain. In other words, reference to a group being a polypropylene group does not require that the group consist of 100% propylene monomers without any linking groups, substitutions, impurities or other substituents (e.g., alkylene or alkenylene substituents). Such impurities or other substituents can be present in relatively minor amounts so long as
they do not affect the industrial performance of the additive, as compared to the same additive containing the respective polymer substituent with 100% purity.
[0025] For the purposes of the present application, when a polymer is referred to as comprising an olefin, the olefin present in the polymer is the polymerized form of the olefin.
[0026] As used herein, a copolymer is a polymer comprising at least two different monomer units (such as propylene and ethylene). A homo-polymer is a polymer comprising units of the same monomer (such as propylene). A propylene polymer is a polymer having at least 50 mole%> of propylene.
[0027] The term "vinyl termination", also referred to as "allyl chain end(s)" or "vinyl content" is defined to be a polymer having at least one terminus represented by:
allylic vinyl end group
where the "····" represents the polymer chain.
allylic vinyl end group
[0029] The amount of allyl chain ends (also called % vinyl termination) is determined using 1H NMR at 120°C using deuterated tetrachloroethane as the solvent on a 500 MHz machine and in selected cases confirmed by 13C NMR. Resconi has reported proton and carbon assignments (neat perdeuterated tetrachloroethane used for proton spectra while a 50:50 mixture of normal and perdeuterated tetrachloroethane was used for carbon spectra; all spectra were recorded at 100°C on a Bruker AM 300 spectrometer operating at 300 MHz for proton and 75.43 MHz for carbon) for vinyl terminated propylene polymers in J American Chemical Soc 114 1992, 1025-1032, hereby incorporated by reference in its entirety, that are useful herein.
[0030] "Isobutyl chain end" is defined to be a polymer having at least one terminus represented by the formula:
where M represents the polymer chain. In an example embodiment, the isobutyl chain end is represented by one of the following formulae:
isobutyl end group
where M represents the polymer chain.
[0031] The "isobutyl chain end to allylic vinyl group ratio" is defined to be the ratio of the
percentage of isobutyl chain ends to the percentage of allylic vinyl groups.
[0032] As used herein, the term "polymer" refers to a chain of monomers having a Mn of
100 g/mol and above.
[0033] Reference will now be made to various aspects of the disclosed subject matter in view of the definitions above.
[0034] In accordance with one aspect of the disclosed subject matter, a method for treating an emulsion of a hydrocarbon is provided. The method includes: (i) providing an emulsion of a crude hydrocarbon, and (ii) adding an additive to the emulsion to obtain a treated hydrocarbon, the additive being represented by one or more of Formula A, B, C, and D below:
(Formula A)
wherein in each of the Formula A, B, C, and D above:
m is an integer between 0 and 10 inclusive;
Ri is a branched or straight-chained Cio-Cgoo alkyl or alkenyl group;
R2 is a C1-C4 branched or straight chained alkylene group;
R3 is a C1-C4 branched or straight chained alkylene group;
R31 is hydrogen or -Rg-Rsi, wherein R8 is C1-C4 branched or straight chained alkylene group, and R9 is
wherein R91 is a branched or straight-chained Cio-Cgoo alkyl or alkenyl group; or R8 and R9 together are a C1-C4 branched or straight chained alkyl group optionally substituted with one or more amine groups; and further wherein the -N(R3i)-R3- repeat unit is optionally interrupted in one or more places by a nitrogen-containing heterocyclic cycloalkyl group; and
R4 and R5 are each independently selected from (a) hydrogen; (b) a bond connected to R31 in the last distal -N(R3i)-R3- repeat unit; or (c) -R5-R7, wherein R6 is C1-C4 branched or straight chained alkylene group, and R7 is
wherein in Formula B, n is an integer between 0 and 10 inclusive, and the groups R2', R3', R3i', R4' and R5' are each defined the same as R2, R3, R3i and R4, and R5, respectively; and wherein in Formula D, z is 1 or 2, and y is an integer between 1 and 5 inclusive.
[0035] In certain embodiments, at least one of Ri, R7i, and R91 of the compounds shown above comprises polypropylene (PP), which can be atactic polypropylene or isotactic polypropylene. The polypropylene can be amorphous, and can include isotactic or syndiotactic crystallizable units. In some embodiments, the polypropylene includes meso diads constituting from about 30% to about 99.5% of the total diads of the polypropylene. In alternative embodiments, at least one of Rls R71, and R91 of the compounds above comprises polyethylene (PE).
[0036] In a further embodiment, at least one of Ri, R7i, and R91 of the compounds above comprises poly(ethylene-co-propylene) (EP). The mole percentage of the ethylene units and propylene units in the poly(ethylene-co-propylene) can vary. For example, in some embodiments, the poly(ethylene-co-propylene) can contain about 1 to about 90 mole % of ethylene units and about 99 to about 10 mole % propylene units. In other embodiments, the
poly(ethylene-co-propylene) can contain about 10 to about 90 mole % of ethylene units and about 90 to about 10 mole % propylene units. In certain embodiments, the poly(ethylene- co-propylene) contains about 20 to about 50 mole% of ethylene units.
[0037] In some embodiments of the above method, at least one of Rls R71, and R91 of the compounds above has a number-averaged molecular weight of from about 300 to about 30,000 g/mol (assuming one olefin unsaturation per chain, as measured by 1H NMR).
Alternatively, at least one of Ri, R71, and R91 of the additive of the compounds above has a number-averaged molecular weight of from about 500 to 5,000 g/mol. In one embodiment, the PP or EP included in the Ri, R71 or R91 of the compounds above, individually, has a molecular weight from about 300 to about 30,000 g/mol, or from about 500 to about 5000 g/mol. In one embodiment, the PP or EP groups have a molecular weight, individually, ranging from about 500 to about 2500 g/mol, or a molecular of from about 500 to about 650 g/mol, or a molecular weight of from about 800 to about 1000 g/mol, or a molecular weight of from about 2000 to about 2500 g/mol.
[0038] In other embodiments of the compounds, at least one of Ri, R71, and R91 comprises poly(higher alpha-olefm) or poly(propylene-co-higher alpha-olefm), the higher alpha-olefm including two or more carbon atoms on each side chain. For example, suitable higher alpha- olefms can include, but are not limited to, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1- octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1- hexadecene, 1-octadecene and the like.
[0039] In certain embodiments of the above compounds, the nitrogen content in the compounds above is about 1 wt% to about 10 wt% based on the total weight of the compound.
[0040] In certain embodiments, R3 is -CH2-CH2-, and R31 is hydrogen. In these
embodiments, the -N(R3i)-R3- repeat unit can be interrupted in one or more places by a 1,4- diethylenediamine.
[0041] With reference now to the compounds of Formula A, U.S. Patent Publication No. 20100170829 provides a detailed description of the compounds and methods of making the compounds. The disclosure of U.S. Patent Publication No. 20100170829 is hereby incorporated by reference in its entirety.
[0042] With reference now to the compounds of Formula C, such compounds can be obtained by the methods disclosed below, where the vinylidene-terminated polymer base unit is reacted with maleic anhydride without a radical initiator. An exemplary protocol for the synthesis of a Formula C intermediate is provided below in Example 1 A, while an exemplary protocol for the condensation of the Formula C intermediate with a polyamine to yield a species of Formula C is disclosed below in Example ID.
[0043] With reference to Formula B, and in accordance with another aspect of the subject matter disclosed herein, a method for preparing a compound for treating an emulsion of crude hydrocarbon in a hydrocarbon refining process is provided. The method includes:
(a) reacting a polymer base unit Rn, which is a branched or straight-chained Ci0-C8oo alkyl or alkenyl group having a vinyl terminal group, with maleic anhydride to obtain a polymer represented by Formula I below:
wherein R2i is a branched or straight-chained Cio-Cgoo alkyl or alkenyl group;
(b) reacting the polymer obtained in a) with a polyamine represented by
wherein Ri2 is hydrogen or a C1-C4 branched or straight chained alkyl optionally substituted with one or more amine groups, R13 is a C1-C4 branched or straight chained alkylene group, and x is an integer between 1 and 10, and further wherein the -N(Ri2)-Ri3- unit is optionally interrupted in one or more places by a nitrogen-containing heterocyclic cycloalkyl group,
and wherein when the x-th -N(Ri2)-Ri3- unit along with the terminal nitrogen atom forms a heterocyclic cycloalkyl group, the terminal -NH2 is replaced by a -NH- group for valency.
[0044] In certain embodiments of the above methods, the polymer base unit Rn has a number-averaged molecular weight of 300 to 30,000 g/mol (assuming one olefin
unsaturation per chain, as measured by 1H NMR), and alternatively, about 500 to 5,000 g/mol.
[0045] In some embodiments of the above methods, the polymer base unit Rn comprises polypropylene. The polypropylene can be either atactic polypropylene or isotactic polypropylene. The polypropylene can be amorphous, and can include isotactic or syndiotactic crystallizable units. In some embodiments, the polypropylene includes meso diads constituting from about 30% to about 99.5% of the total diads of the polypropylene. The polymer base unit Rn can also comprise polyethylene.
[0046] In alternative embodiments, the polymer base unit Rn comprises poly(ethylene-co- propylene). The poly(ethylene-co-propylene) can contain from about 1 or 10 mole% to about 90 or 99 mole% of ethylene units and from about 99 or 90 mole% to about 10 or 1 mole% propylene units. In one embodiment, the poly(ethylene-co-propylene) polymer contains from about 2 or 20 mole% to about 50 mole% ethylene units.
[0047] In one embodiment, the PP or EP included in Rn to form Formula I individually has a number-averaged molecular weight ( n) molecular weight from about 300 to about 30,000 g/mol, or from about 500 to about 5000 g/mol (assuming one olefin unsaturation per chain, as measured by 1H NMR). In one embodiment, the PP or EP groups have a molecular weight, individually, ranging from about 500 to about 2500 g/mol, or a molecular of from about 500 to about 650 g/mol, or a molecular weight of from about 800 to about 1000 g/mol, or a molecular weight of from about 2000 to about 2500 g/mol.
[0048] In embodiments where the polymer base unit Rn includes polypropylene or poly(ethylene-co-propylene), such groups can be prepared, for example, by metallocene- catalyzed polymerization of propylene or a mixture of ethylene and propylene, which are then terminated with a high vinyl group content in the chain end. The number-averaged molecular weight ( n) of the PP or EP can be from about 300 to about 30,000 g/mol, as determined by 1H NMR spectroscopy. The vinyl-terminated atactic or isotactic
polypropylenes (v-PP) or vinyl-terminated poly(ethylene-co-propylene) (v-EP) suitable for further chemical functionalization can have a molecular weight ( n) approximately from about 300 to about 30,000 g/mol, and preferably about 500 to 5,000 g/mol. The terminal olefin group can be a vinylidene group or an allylic vinyl group (both covered in Formula I). In certain embodiments, the terminal olefin group is an allylic vinyl group. In this regard, the terminal allylic vinyl group rich PP or EP as disclosed in U.S. Patent No. 8,372,930 and U.S Patent Application Publication No. 20090318646, can be used, which are both hereby incorporated by reference in their entirety. Some of the vinyl terminated EP or PP according to these co-pending applications contains more than 90 % of allylic terminal vinyl group.
[0049] In some embodiments of the above methods, Rn can comprise propylene and less than 0.5 wt% comonomer, preferably 0 wt% comonomer, wherein the Rn has:
i) at least 93% allyl chain ends (preferably at least 95%, preferably at least 97%, preferably at least 98%);
ii) a number average molecular weight (Mn) of about 500 to about 20,000 g/mol, as measured by 1H NMR, assuming one olefin unsaturation per chain (preferably 500 to 15,000, preferably 700 to 10,000, preferably 800 to 8,000 g/mol, preferably 900 to 7,000, preferably 1000 to 6,000, preferably 1000 to 5,000); iii) an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.3: 1.0;
iv) less than 1400 ppm aluminum, (preferably less than 1200 ppm, preferably less than 1000 ppm, preferably less than 500 ppm, preferably less than 100 ppm).
[0050] In some embodiments of the above methods, Rn can comprise a propylene copolymer having an Mn of 300 to 30,000 g/mol as measured by 1H NMR and assuming one olefin unsaturation per chain (preferably 400 to 20,000, preferably 500 to 15,000, preferably 600 to 12,000, preferably 800 to 10,000, preferably 900 to 8,000, preferably 900 to 7,000 g/mol), comprising 10 to 90 mol% propylene (preferably 15 to 85 mol%, preferably 20 to 80 mol%, preferably 30 to 75 mol%, preferably 50 to 90 mol%) and 10 to 90 mol% (preferably 85 to 15 mol%, preferably 20 to 80 mol%, preferably 25 to 70 mol%, preferably 10 to 50 mol%) of one or more alpha-olefin comonomers (preferably ethylene, butene, hexene, or octene, or decene, preferably ethylene), wherein the polymer has at least X% allyl chain ends (relative to total unsaturations), where X is 80% or more, preferably 85% or
more, preferably 90% or more, preferably 95% or more. Alternatively, Rn can have at least 80%) isobutyl chain ends (based upon the sum of isobutyl and n-propyl saturated chain ends), preferably at least 85% isobutyl chain ends, preferably at least 90%> isobutyl chain ends. Alternately, Rn can have an isobutyl chain end to ally lie vinyl group ratio of 0.8: 1 to 1.35:1.0, preferably 0.9: 1 to 1.20: 1.0, preferably 0.9: 1.0 to 1.1 : 1.0.
[0051] In other embodiments, Rn can comprise a polypropylene copolymer having more than 90 mol% propylene (preferably 95 to 99 mol%, preferably 98 to 9 mol%) and less than 10 mol% ethylene (preferably 1 to 4 mol%, preferably 1 to 2 mol%), wherein the copolymer has:
at least 93% allyl chain ends (preferably at least 95%, preferably at least 97%, preferably at least 98%);
a number average molecular weight (Mn) of about 400 to about 30,000 g/mol, as measured by 1H NMR and assuming one olefin unsaturation per chain (preferably 500 to 20,000, preferably 600 to 15,000, preferably 700 to 10,000 g/mol, preferably 800 to 9,000, preferably 900 to 8,000, preferably 1000 to 6,000);
an isobutyl chain end to ally lie vinyl group ratio of 0.8: 1 to 1.35: 1.0, and
less than 1400 ppm aluminum, (preferably less than 1200 ppm, preferably less than 1000 ppm, preferably less than 500 ppm, preferably less than 100 ppm).
[0052] In alternative embodiments, Rn can comprise a polypropylene copolymer comprising:
at least 50 (preferably 60 to 90, preferably 70 to 90) mol% propylene and from 10 to 50 (preferably 10 to 40, preferably 10 to 30) mol% ethylene, wherein the polymer has:
at least 90% allyl chain ends (preferably at least 91%, preferably at least 93%, preferably at least 95%, preferably at least 98%);
an Mn of about 150 to about 20,000 g/mol, as measured by 1H NMR and assuming one olefin unsaturation per chain (preferably 200 to 15,000, preferably 250 to 15,000, preferably 300 to 10,000, preferably 400 to 9,500, preferably 500 to 9,000, preferably 750 to 9,000); and
an isobutyl chain end to ally lie vinyl group ratio of 0.8: 1 to 1.3: 1.0, wherein monomers having four or more carbon atoms are present at from 0 to 3 mol% (preferably at
less than 1 mol%, preferably less than 0.5 mol%, preferably at 0 mol%).
[0053] In further embodiments, Rn can comprise a polypropylene copolymer comprising: at least 50 (preferably at least 60, preferably 70 to 99.5, preferably 80 to 99, preferably 90 to 98.5) mol% propylene, from 0.1 to 45 (preferably at least 35, preferably 0.5 to 30, preferably 1 to 20, preferably 1.5 to 10) mol% ethylene, and from 0.1 to 5 (preferably 0.5 to 3, preferably 0.5 to 1) mol% C4 to C12 olefin (such as butene, hexene or octene, or decene, preferably butene), wherein the polymer has:
at least 90% allyl chain ends (preferably at least 91%, preferably at least 93%, preferably at least 95%, preferably at least 98%);
a number average molecular weight (Mn) of about 150 to about 15,000 g/mol, as measured by 1H NMR and assuming one olefin unsaturation per chain (preferably 200 to 12,000, preferably 250 to 10,000, preferably 300 to 10,000, preferably 400 to 9500, preferably 500 to 9,000, preferably 750 to 9,000); and
an isobutyl chain end to ally lie vinyl group ratio of 0.8: 1 to 1.35: 1.0.
[0054] In certain embodiments, Rn can comprise a polypropylene copolymer comprising: at least 50 (preferably at least 60, preferably 70 to 99.5, preferably 80 to 99, preferably 90 to 98.5) mol% propylene, from 0.1 to 45 (preferably at least 35, preferably 0.5 to 30, preferably 1 to 20, preferably 1.5 to 10) mol% ethylene, and from 0.1 to 5 (preferably 0.5 to 3, preferably 0.5 to 1) mol% diene (such as C4 to C12 alpha-omega dienes (such as butadiene, hexadiene, octadiene), norbornene, ethylidene norbornene, vinylnorbornene, norbornadiene, and dicyclopentadiene), wherein the polymer has:
at least 90% allyl chain ends (preferably at least 91%, preferably at least 93%, preferably at least 95%, preferably at least 98%);
a number average molecular weight (Mn) of about 150 to about 20,000 g/mol, as measured by 1H NMR and assuming one olefin unsaturation per chain (preferably 200 to 15,000, preferably 250 to 12,000, preferably 300 to 10,000, preferably 400 to 9,500, preferably 500 to 9,000, preferably 750 to 9,000); and
an isobutyl chain end to ally lie vinyl group ratio of 0.7: 1 to 1.35: 1.0.
[0055] In other embodiments of the above methods, Rn can comprise poly(higher alpha- olefin) or poly(propylene-co-higher alpha-olefin), the higher alpha-olefin including two or
more carbon atoms on each side chain. For example, suitable higher alpha-olefms can include, but are not limited to, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1- nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-hexadecene, 1- octadecene and the like.
[0056] In certain embodiments, Rn includes those vinyl terminated macromonomers disclosed in U.S. Patent Application Publication Nos. 20120245312, 20120245310, 20120245311, 20120245313, and U.S. Provisional Application No. 61/704,604, the disclosure of each of which is incorporated by reference in its entirety herein.
[0057] In the above method of preparation, maleic anhydride can be used for the reaction of converting a polymer base unit Rn having a terminal vinyl functionality to a compound of Formula I. The reaction can proceed through a thermal condition (e.g., at temperature of about 150°C to 260°C) without using external radical providers, such as a peroxide initiator. Under this condition, a compound of Formula I can be obtained, along with a polymer having a mono-succinic anhydride terminal group. For example and as embodied herein, the thermal reaction between Rn and maleic anhydride can be illustrated below in Scheme 1 using a vinyl terminated polypropylene as an example of Rn.
pro
polypropylene di-succinic anhydride
Scheme 1
[0058] The above reaction can be carried out without the use of any solvent. Alternatively, any inert solvent (e.g., paraffinic solvent, naphthenic solvent, aromatic solvent, halogenated solvent, mineral oil, synthetic fluid, etc.) with appropriate boiling point or boiling point
range can be used. The reaction can be conducted in an open system under atmospheric pressure by using standard laboratory glassware or in a closed system by using an autoclave (or any sealed vessel suitable for maintaining pressure). A catalyst can also be used to
increase the rate of reaction between the hydrocarbon copolymer and the unsaturated
carboxylic acid derivative.
[0059] The vinyl terminated polymer can also be a copolymer of polypropylene, for
example, poly-ethylene-propylene, or poly-propylene-higher alpha-olefm. In such cases, the reactions under a thermal condition can be illustrated below in Scheme 2 and Scheme 3,
respectively.
ethylene-propylene copolymer di-succinic anhydride
Scheme 2
mono-succinic anhydride propylene-higher alpha olefin copolymer di-succinic anhydride
Scheme 3
[0060] The above reactions can be performed at temperatures between about 150 °C to about 260 °C and between about atmospheric pressure to about 500 psi. The reaction can be conducted in an open system under atmospheric pressure by using standard laboratory
glassware or in a closed system by using an autoclave (or any sealed vessel suitable for
maintaining pressure). Reaction time can vary from minutes to hours depending on the conditions used. The rate of reaction will increase with increased temperature and pressure. At temperatures between about 220-260 °C at elevated pressure, high conversion of the vinyl-terminated polymers can be achieved within about two hours.
[0061] The charge ratio of vinyl-terminated polymers to maleic anhydride in the reactions depicted in Scheme 1 , Scheme 2 and Scheme 3 can vary from about 1 : 1 to about 1 : 10, or preferably from about 1 : 1 to about 1 :6, or preferably from about 1 : 1 to about 1 :4, or preferably from about 1 : 1 to about 1 :3, or preferably from about 1 : 1 to about 1 :2, or preferably from about 1 : 1 to about 1 : 1.5, or preferably from about 1 : 1 to about 1 : 1.2.
Increasing the charge ratio of maleic anhydride to vinyl-terminated polymer will increase the proportion of di-succinic anhydride product and decrease the proportion of mono- succinic anhydride product. Additionally, at a given temperature, increasing the reaction time will increase the proportion of di-succinic anhydride reaction products relative to mono-succinic anhydride products, provided that sufficient maleic anhydride is present in the reaction system.
[0062] The method of preparing the compound B can include reacting the succinic anhydride-containing polymers obtained above with a polyamine (PAM). The reaction can proceed through a condensation mechanism. The polyamine can include linear, branched or cyclic isomers of an oligomer of ethyleneamine, or mixtures thereof, wherein each two neighboring nitrogens in the oligomer of ethyleneamine are bridged by one or two ethyleneamine groups. For example, the polyamine can be selected from
polyethyleneamines with general molecular formula Η2Ν( Η2 ¾ΝΗ)ΧΗ (where x = 1, 2, 3, ...) such as ethylenediamine, diethylenetriamine, triethylenetetramine,
tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, and mixtures thereof. In some embodiments, the polyamine can comprise a heavy polyamine, such as poly ethyleneamine heavy bottoms available from Dow Chemical as "Heavy Polyamine X" or HPA-X.
[0063] Using a reaction between the products of Scheme 3 and tetraethylenepentamine as an example of PAM, the condensation reaction can be illustrated below in Scheme 4.
Scheme 4
[0064] In additional embodiments of the disclosed subject matter, nucleophilic reagents other than polyamines can be used to functionalize the compounds of Formula I. These reagents include, for example, monoamines, diamines, amino alcohols, polyetheramines, polyols, polyalkylene glycols, polyalkylene polyamine and the like.
[0065] Furthermore, vinylidene-terminated polymer or copolymer (e.g., ethylene-propylene copolymer, and propylene-higher alpha-olefm copolymer) can also be used as Rn.
Illustrations for using vinylidene-terminated polypropylene and vinylidene-terminated propylene-higher alpha-olefm copolymer as Rn are shown below in Scheme 5 and Scheme 6, respectively.
PP = polypropylene
Scheme 5
Copolymer
vinylidene-terminated macromer Copolymer-SA-TEPA Copolymer = C3/Cn copolymer
[0066] As a result of the animation reactions, the number of polymer chain attached to each polyamine molecule can vary from one to two to three or more. In addition, both primary and secondary amino groups on the polyamine can participate in the reaction with the anhydride-functionalized polymer. Other commercially available lower or higher polyamines with linear, branched, cyclic or heterocyclic structures can also be used. It is well-known and understood by those skilled in the art that these polyamines can be mixtures of compounds comprised of molecules with a distribution of chain lengths, different level and type of amine (primary, secondary, and tertiary) functional groups, and varying degree of linear, branched and cyclic structures. For example, possible isomers for
tetraethylenepentamine include the following:
As the molecular weight of polyamines increases, the number of possible isomers increases as well.
[0067] In a further aspect, a method for preparing a compound according to Formula D for treating an emulsion of crude hydrocarbon in a hydrocarbon refining process is provided. The method includes:
(a) reacting a polymer base unit Rn, which is a branched or straight-chained Cio-Cgoo alkyl or alkenyl group having a vinyl terminal group, with maleic anhydride in the presence of a radical initiator to obtain a olymer represented by Formula II below:
(II)
wherein R2i is a branched or straight-chained Ci0-C8oo alkyl or alkenyl group, z is 1 or 2, and y is an integer between 1 and 5 inclusive;
(b) reacting the polymer obtained in a) with a polyamine represented by
[0068] wherein Ri2 is hydrogen or a C1-C4 branched or straight chained alkyl optionally substituted with one or more amine groups, R13 is a C1-C4 branched or straight chained alkylene group, and x is an integer between 1 and 10, and further wherein the -N(Ri2)-Ri3- unit is optionally interrupted in one or more places by a nitrogen-containing heterocyclic cycloalkyl group, and wherein when the x-th -N(Ri2)-Ri3- unit along with the terminal nitrogen atom forms a heterocyclic cycloalkyl group, the terminal -NH2 is replaced by a - NH- group for valency.
[0069] In certain embodiments of the above methods, the polymer base unit Rn has a number-averaged molecular weight of 300 to 30,000 g/mol (assuming one olefin
unsaturation per chain, as measured by 1H NMR), and alternatively, about 500 to 5,000 g/mol.
[0070] In some embodiments of the above methods, the polymer base unit Rn comprises polypropylene. The polypropylene can be either atactic polypropylene or isotactic polypropylene. The polypropylene can be amorphous, and can include isotactic or
syndiotactic crystallizable units. In some embodiments, the polypropylene includes meso diads constituting from about 30% to about 99.5% of the total diads of the polypropylene. The polymer base unit Rn can also comprise polyethylene.
[0071] In alternative embodiments, the polymer base unit Rn comprises poly(ethylene-co- propylene). The poly(ethylene-co-propylene) can contain from about 1 or 10 mole% to about 90 or 99 mole% of ethylene units and from about 99 or 90 mole% to about 10 or 1 mole% propylene units. In one embodiment, the poly(ethylene-co-propylene) polymer contains from about 2 or 20 mole% to about 50 mole% ethylene units.
[0072] In one embodiment, the PP or EP included in the Rn to form Formula II individually has a number-averaged molecular weight ( n) from about 300 to about 30,000 g/mol, or from about 500 to about 5000 g/mol (assuming one olefin unsaturation per chain, as measured by 1H NMR). In one embodiment, the PP or EP groups have a molecular weight, individually, ranging from about 500 to about 2500 g/mol, or a molecular of from about 500 to about 650 g/mol, or a molecular weight of from about 800 to about 1000 g/mol, or a molecular weight of from about 2000 to about 2500 g/mol.
[0073] In embodiments where the polymer base unit Rn include polypropylene or poly(ethylene-co-propylene), such groups can be prepared, for example, by metallocene- catalyzed polymerization of propylene or a mixture of ethylene and propylene, which are then terminated with a high vinyl group content in the chain end. The number-averaged molecular weight ( n) of the PP or EP can be from about 300 to about 30,000 g/mol, as determined by 1H NMR spectroscopy. The vinyl-terminated atactic or isotactic
polypropylenes (v-PP) or vinyl-terminated poly(ethylene-co-propylene) (v-EP) suitable for further chemical functionalization can have a molecular weight ( n) approximately from about 300 to about 30,000 g/mol, and preferably about 500 to 5,000 g/mol. The terminal olefin group can be a vinylidene group or an allylic vinyl group. In certain embodiments, the terminal olefin group is an allylic vinyl group. In this regard, the terminal allylic vinyl group rich PP or EP as disclosed in U.S. Patent No. 8,372,930 and co-pending application, U.S. Patent Application Publication No. 20090318646, can be used, each of which is hereby incorporated by reference in its entirety. Some of the vinyl terminated EP or PP according to these co-pending applications contains more than 90 % of allylic terminal vinyl group.
[0074] In some embodiments of the above methods, Rn can comprise propylene and less than 0.5 wt% comonomer, preferably 0 wt% comonomer, wherein the Rn has:
i) at least 93% allyl chain ends (preferably at least 95%>, preferably at least 97%>, preferably at least 98%>);
ii) a number average molecular weight (Mn) of about 500 to about 20,000 g/mol, as measured by 1H NMR, assuming one olefin unsaturation per chain (preferably 500 to 15,000, preferably 700 to 10,000, preferably 800 to 8,000 g/mol, preferably 900 to 7,000, preferably 1000 to 6,000, preferably 1000 to 5,000); iii) an isobutyl chain end to ally lie vinyl group ratio of 0.8: 1 to 1.3: 1.0;
iv) less than 1400 ppm aluminum, (preferably less than 1200 ppm, preferably less than 1000 ppm, preferably less than 500 ppm, preferably less than 100 ppm).
[0075] In some embodiments of the above methods, Rn can comprise a propylene copolymer having an Mn of 300 to 30,000 g/mol as measured by 1H NMR and assuming one olefin unsaturation per chain (preferably 400 to 20,000, preferably 500 to 15,000, preferably 600 to 12,000, preferably 800 to 10,000, preferably 900 to 8,000, preferably 900 to 7,000 g/mol), comprising 10 to 90 mol%> propylene (preferably 15 to 85 mol%>, preferably 20 to 80 mol%, preferably 30 to 75 mol%, preferably 50 to 90 mol%) and 10 to 90 mol% (preferably 85 to 15 mol%>, preferably 20 to 80 mol%>, preferably 25 to 70 mol%>, preferably 10 to 50 mol%) of one or more alpha-olefin comonomers (preferably ethylene, butene, hexene, or octene, or decene, preferably ethylene), wherein the polymer has at least X% allyl chain ends (relative to total unsaturations), where X is 80% or more, preferably 85% or more, preferably 90% or more, preferably 95% or more. Alternatively, Rn can have at least 80%) isobutyl chain ends (based upon the sum of isobutyl and n-propyl saturated chain ends), preferably at least 85%> isobutyl chain ends, preferably at least 90%> isobutyl chain ends. Alternately, Rn can have an isobutyl chain end to ally lie vinyl group ratio of 0.8: 1 to 1.35:1.0, preferably 0.9: 1 to 1.20: 1.0, preferably 0.9: 1.0 to 1.1 : 1.0.
[0076] In other embodiments, Rn can comprise a polypropylene copolymer having more than 90 mol% propylene (preferably 95 to 99 mol%, preferably 98 to 9 mol%) and less than 10 mol% ethylene (preferably 1 to 4 mol%, preferably 1 to 2 mol%), wherein the copolymer has:
at least 93% allyl chain ends (preferably at least 95%, preferably at least 97%, preferably at least 98%);
a number average molecular weight (Mn) of about 400 to about 30,000 g/mol, as measured by 1H NMR and assuming one olefin unsaturation per chain (preferably 500 to 20,000, preferably 600 to 15,000, preferably 700 to 10,000 g/mol, preferably 800 to 9,000, preferably 900 to 8,000, preferably 1000 to 6,000);
an isobutyl chain end to ally lie vinyl group ratio of 0.8: 1 to 1.35: 1.0, and
less than 1400 ppm aluminum, (preferably less than 1200 ppm, preferably less than 1000 ppm, preferably less than 500 ppm, preferably less than 100 ppm).
[0077] In alternative embodiments, Rn can comprise a polypropylene copolymer comprising:
at least 50 (preferably 60 to 90, preferably 70 to 90) mol% propylene and from 10 to 50 (preferably 10 to 40, preferably 10 to 30) mol% ethylene, wherein the polymer has:
at least 90% allyl chain ends (preferably at least 91%, preferably at least 93%, preferably at least 95%, preferably at least 98%);
an Mn of about 150 to about 20,000 g/mol, as measured by 1H NMR and assuming one olefin unsaturation per chain (preferably 200 to 15,000, preferably 250 to 15,000, preferably 300 to 10,000, preferably 400 to 9,500, preferably 500 to 9,000, preferably 750 to 9,000); and
an isobutyl chain end to ally lie vinyl group ratio of 0.8: 1 to 1.3: 1.0, wherein monomers having four or more carbon atoms are present at from 0 to 3 mol% (preferably at less than 1 mol%, preferably less than 0.5 mol%, preferably at 0 mol%).
[0078] In further embodiments, Rn can comprise a polypropylene copolymer comprising: at least 50 (preferably at least 60, preferably 70 to 99.5, preferably 80 to 99, preferably 90 to 98.5) mol% propylene, from 0.1 to 45 (preferably at least 35, preferably 0.5 to 30, preferably 1 to 20, preferably 1.5 to 10) mol% ethylene, and from 0.1 to 5 (preferably
0.5 to 3, preferably 0.5 to 1) mol% C4 to C12 olefin (such as butene, hexene or octene, or decene, preferably butene), wherein the polymer has:
at least 90% allyl chain ends (preferably at least 91%, preferably at least 93%, preferably at least 95%, preferably at least 98%);
a number average molecular weight (Mn) of about 150 to about 15,000 g/mol, as measured by 1H NMR and assuming one olefin unsaturation per chain (preferably 200 to 12,000, preferably 250 to 10,000, preferably 300 to 10,000, preferably 400 to 9500, preferably 500 to 9,000, preferably 750 to 9,000); and
an isobutyl chain end to ally lie vinyl group ratio of 0.8: 1 to 1.35: 1.0.
[0079] In certain embodiments, Rn can comprise a polypropylene copolymer comprising: at least 50 (preferably at least 60, preferably 70 to 99.5, preferably 80 to 99, preferably 90 to 98.5) mol% propylene, from 0.1 to 45 (preferably at least 35, preferably 0.5 to 30, preferably 1 to 20, preferably 1.5 to 10) mol% ethylene, and from 0.1 to 5 (preferably 0.5 to 3, preferably 0.5 to 1) mol% diene (such as C4 to C12 alpha-omega dienes (such as butadiene, hexadiene, octadiene), norbornene, ethylidene norbornene, vinylnorbornene, norbornadiene, and dicyclopentadiene), wherein the polymer has:
at least 90% allyl chain ends (preferably at least 91%, preferably at least 93%, preferably at least 95%, preferably at least 98%);
a number average molecular weight (Mn) of about 150 to about 20,000 g/mol, as measured by 1H NMR and assuming one olefin unsaturation per chain (preferably 200 to 15,000, preferably 250 to 12,000, preferably 300 to 10,000, preferably 400 to 9,500, preferably 500 to 9,000, preferably 750 to 9,000); and
an isobutyl chain end to ally lie vinyl group ratio of 0.7: 1 to 1.35: 1.0.
[0080] In other embodiments of the above methods, Rn can comprise poly(higher alpha- olefin) or poly(propylene-co-higher alpha-olefin), the higher alpha-olefin including two or more carbon atoms on each side chain. For example, suitable higher alpha-olefms can include, but are not limited to, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1- nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-hexadecene, 1- octadecene and the like.
[0081] In certain embodiments, Rn includes those vinyl terminated macromonomers disclosed in U.S. Patent Application Publication Nos. 20120245312, 20120245310, 20120245311, 20120245313, and U.S. Provisional Application No. 61/704,604, the disclosure of each of which is incorporated by reference in its entirety herein.
[0082] In the disclosed method of preparation of Compound D, maleic anhydride can be used for the reaction of converting a polymer base unit Rn having a terminal vinyl functionality to a compound of Formula II. The reaction between Rn and maleic anhydride can be initiated by a radical initiator. The reaction under this condition can result in
Formula II noted above as illustrated below in Scheme 7:
Scheme 7
[0083] The vinyl-terminated polymer and maleic anhydride can be mixed either neat or in an inert solvent (e.g., paraffmic solvent, naphthenic solvent, aromatic solvent, halogenated solvent, mineral oil, synthetic fluid, etc.) with appropriate boiling point or boiling point range. The reaction can be conducted in an open system under atmospheric pressure by using standard laboratory glassware or in a closed system by using an autoclave (or any sealed vessel suitable for holding the pressure). The temperature can vary from 80 to 180
C, or preferably from 100 to 170 C, or preferably from 120 to 170 °C, or preferably from 130 to 170 °C. Reactant charge ratio of vinyl-terminated polymer to maleic anhydride can
vary from about 1 : 1 to about 1 :4, or from about 1 : 1 to about 1 :3, or from about 1 : 1 to about 1 :2, or from about 1 : 1 to about 1 : 1.5, or from about 1 : 1 to about 1 : 1.2. Suitable radical initiators include, but not limited to, organic peroxides such as di-tert-butyl peroxide, dicumyl peroxide, lauroyl peroxide, benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxybenzoate (peroxy ester), tert-butyl peracetate (peroxy ester), 2,2'-azobisisobutyronitrile (AIBN), 1 , -azobis(cyclohexanecarbonitrile) or similar diazo compounds. The radical initiator can be introduced in portions over a convenient period of time, if desired for controlling reaction rate, to the mixture of vinyl-terminated polymer and maleic anhydride at a suitable temperature (e.g., from about 120 to 165 °C for di-tert-butyl peroxide) needed for thermal decomposition of the radical initiator to generate radical species at a rate suitable for the reaction.
[0084] As previously noted, the method of preparing the compounds can include reacting the succinic anhydride-containing polymers obtained above with a polyamine. The reaction can proceed through a condensation mechanism. The polyamine can include linear, branched or cyclic isomers of an oligomer of ethyleneamine, or mixtures thereof, wherein each two neighboring nitrogens in the oligomer of ethyleneamine are bridged by one or two ethyleneamine groups. For example, the polyamine can be selected from
polyethyleneamines with general molecular formula H2N(CH2CH2NH)XH (where x = 1, 2, 3, ...) such as ethylenediamine, diethylenetriamine, triethylenetetramine,
tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, and mixtures thereof. In some embodiments, the polyamine can comprise a heavy polyamine, such as poly ethyleneamine heavy bottoms available from Dow Chemical as "Heavy Polyamine X" or HPA-X.
[0085] Using a reaction between the products of Scheme 7 and tetraethylenepentamine as an exemplary polyamine, the condensation reaction can be illustrated below in Scheme 8.
Scheme 8
[0086] In alternative embodiments, nucleophilic reagents other than polyamines can be used to functionalize the compounds of Formula II. These reagents include, for example, monoamines, diamines, amino alcohols, polyetheramines, polyols, polyalkylene glycols, polyalkylene poly amine and the like.
[0087] Furthermore, vinylidene-terminated polymer or copolymer (e.g., ethylene-propylene copolymer, and propylene-higher alpha-olefm copolymer) can also be used as Rn.
Illustrations for using vinylidene-terminated polypropylene and vinylidene-terminated propylene-higher alpha-olefm copolymer as Rn are shown below in Scheme 9 and Scheme 10, respectively
radical initiator
vinylidene-terminated macromer
Scheme 9 radical initiator
vinylidene-terminated macromer
Scheme 10
[0088] As a result of the animation reactions, the number of polymer chain attached to each polyamine molecule can vary from one to two to three or more. In addition, both primary and secondary amino groups on the polyamine can participate in the reaction with the anhydride-functionalized polymer. Other commercially available lower or higher polyamines with linear, branched, cyclic or heterocyclic structures can also be used. It is well-known and understood by those skilled in the art that these polyamines can be mixtures of compounds comprised of molecules with a distribution of chain lengths, different level and type of amine (primary, secondary, and tertiary) functional groups, and varying degree of linear, branched and cyclic structures. For example, possible isomers for
tetraethylenepentamine include the following:
As the molecular weight of polyamines increases, the number of possible isomers increases as well.
[0089] In another aspect of the disclosed subject matter, compounds (additives) prepared by the method discussed above and various embodiments thereof are provided.
[0090] In another aspect, a method for demulsifying a crude hydrocarbon emulsion in a hydrocarbon refining process is provided, which comprises providing an emulsion of a crude hydrocarbon, and adding an additive to the emulsion to obtain a treated hydrocarbon, the additive being represented by one or more of Formula A, B, C, and D above.
[0091] Another aspect of the disclosed subject matter provides a system for refining hydrocarbons that includes at least one crude hydrocarbon refinery component, in which the crude hydrocarbon refinery component includes a compound selected from any one of the compounds described herein. The crude hydrocarbon refining component can be selected from a heat exchanger, a furnace, a crude preheater, a coker preheater, a FCC slurry bottom, a debutanizer exchanger, a debutanizer tower, a feed/effluent exchanger, a furnace air
preheater, a flare compressor component, a steam cracker, a steam reformer, a distillation column, a fractionation column, a scrubber, a reactor, a liquid-jacketed tank, a pipestill, a coker, and a visbreaker. For example, the crude hydrocarbon refining component can be a desalter. Such methods and systems are described in greater details in the following sections and examples.
Uses of the Additives and Compositions For Hydrocarbon Emulsion Treatment
[0092] The additives of the disclosed subject matter are generally soluble in a typical hydrocarbon refinery stream and can thus be added directly to the process stream, alone or in combination with other additives that promote demulsification or improve some other process parameter.
[0093] The additives can be introduced, for example, upstream from the particular crude hydrocarbon refinery component(s) (e.g., a desalter) in which it is desired to promote demulsification (e.g. separation of water and crude). Alternatively, the additive can be added to the crude oil prior to being introduced to the refining process, or at the very beginning of the refining process.
[0094] While not limited thereto, the additives of the disclosed subject matter are
particularly suitable in promoting demulsification of crude hydrocarbon emulsions. Thus one aspect of the disclosed subject matter provides a method of demulsifying, in particular, crude hydrocarbon emulsions that includes adding at least one additive of the disclosed subject matter to a process stream after mixture of the stream with water to extract salts and foulants. In some embodiments of the disclosed subject matter, a method to promote demulsification is provided comprising adding any one of the above-mentioned additives or compositions to a crude hydrocarbon refinery component that is in fluid communication with a process stream that contains a crude hydrocarbon emulsion.
[0095] The total amount of additive to be added to the process stream can be determined by a person of ordinary skill in the art. In one embodiment, up to about 1000 wppm of additive is added to the process stream. For example, the additive can be added such that its concentration, upon addition, is about 50 ppm, 250 ppm or 500 ppm. More or less additive can be added depending on, for example, the degree of demulsification desired in view of
the cost of the additive.
[0096] The additives or compositions of the disclosed subject matter can be added in a solid (e.g. powder or granules) or liquid form directly to the process stream. Any suitable technique can be used for adding the additive to the process stream, as known by a person of ordinary skill in the art in view of the process to which it is employed. As a non-limiting example, the additives or compositions can be introduced via injection that allows for sufficient mixing of the additive and the process stream.
[0097] Figure 1 demonstrates possible additive injection points within the refinery crude pre-heat train for the additives of the disclosed subject matter, wherein the numbered circles represent heat exchangers. As shown in Figure 1, the additives can be introduced in crude storage tanks and at several locations in the preheat train. This includes at the crude charge pump (at the very beginning of the crude pre-heat train), and/or before the desalter or dehydrator. It is contemplated that the additive may be added at any point prior to the crude oil entering the desalter unit.
[0098] The additives or compositions of the disclosed subject matter can be added in a solid (e.g. powder or granules) or liquid form directly to the process stream. As mentioned above, the additives or compositions can be added alone, or combined with other components to form a composition for demulsification. Any suitable technique can be used for adding the additive to the process stream, as known by a person of ordinary skill in the art in view of the process to which it is employed. As a non-limiting example, the additives or
compositions can be introduced via injection that allows for sufficient mixing of the additive and the process stream.
* * *
Examples
[0099] The disclosed subject matter is further described by means of the examples, presented below. The use of such examples is illustrative only and in no way limits the scope and meaning of the disclosed subject matter or of any exemplified term. Likewise, the disclosed subject matter is not limited to any particular preferred embodiments described herein. Indeed, many modifications and variations of the disclosed embodiments will be apparent to those skilled in the art upon reading this specification.
Example 1 - Synthesis of Compounds
Various examples of using the methods of compound synthesis described above are provided herein.
Example 1A: Maleation of vinylidene-terminated polyisobutylene (PIB) with maleic anhydride
[00100] To a 300 ml stainless steel autoclave equipped with a mechanical stirrer and
N2 inlet and an N2 outlet was added highly reactive polyisobutylene (BASF Glissopal 2300, 85 g) followed by maleic anhydride (15.65 g, 159.6 mmol) at room temperature. The mixture was stirred and flushed three times with nitrogen at room temperature and pressurized to 80 psi. The mixture was heated to 250 °C for 2 hours and allowed to cool to room temperature. The pressure was released slowly and the autoclave was opened. The mixture was diluted with hexanes, filtered under house vacuum and the filtrate was concentrated on a rotary evaporator. The mixture was heated at 95 °C under high vacuum to afford a viscous light brown oily product (90.66 g). Elemental analyses for this PIB-SA material found C: 82.44%, H: 13.25%. The oxygen content of this material is estimated to be about 4.31 wt% by difference. The anhydride content of this polymer material is estimated to be about 0.898 mmol/g. Based on the molecular weight of polymer starting material, there is an average of 2.10 succinic anhydride functionality per polymer chain.
Example IB: Maleation of vinyl-terminated polypropylene (vt-PP) with maleic anhydride
[00101] A mixture of vinyl-terminated polypropylene (1H NMR Mn 1210 g/mol,
44.00 g) and maleic anhydride (10.70 g, 109.1 mmol) was heated at 205 °C for 24 hours under a nitrogen atmosphere. The mixture was cooled to room temperature, diluted with hexanes, filtered and concentrated on a rotary evaporator. Excess maleic anhydride was removed by heating under high vacuum to afford a viscous brown oily product (46.59 g). Elemental analyses for this PP-SA material found C: 81.27%, H: 13.19%. The oxygen content of this material is estimated to be about 5.54 wt% by difference. The anhydride content of this polymer material is estimated to be about 1.154 mmol/g. Based on the
molecular weight of polymer starting material, there is an average of 1.55 succinic anhydride functionality per polymer chain.
Example 1C. Maleation of vinyl-terminated propylene/l-hexene copolymer with maleic anhydride
[00102] A mixture of vinyl-terminated propylene/l-hexene copolymer (1H NMR Mn
1638 g/mol, 48.60 g) and maleic anhydride (11.64 g, 118.7 mmol) was heated at 190 °C for 42 hours under a nitrogen atmosphere. The mixture was cooled to room temperature, diluted with hexanes, filtered and concentrated on a rotary evaporator. Excess maleic anhydride was removed by heating under high vacuum to afford a viscous brown oily product (53.10 g). Elemental analyses for this C3C6-SA material found C: 82.33%, H: 13.26%. The oxygen content of this material is estimated to be about 4.41 wt% by difference. The anhydride content of this polymer material is estimated to be about 0.919 mmol/g. Based on the molecular weight of polymer starting material, there is an average of 1.66 succinic anhydride functionality per polymer chain.
Example ID. Condensation of polyisobutylene succinic anhydride (PIB-SA) with tetraethylenepentamine (TEPA)
[00103] A mixture of polyisobutylene succinic anhydride from Example 1A (25.00 g,
22.45 mmol anhydride) and xylenes (100 ml) was stirred at room temperature under a nitrogen atmosphere and a solution of tetraethylenepentamine (2.36 g, 12.47 mmol) in xylenes (15 ml) was slowly added. The resulting mixture was heated in an oil bath at 165 °C for 15.5 hours. The brown mixture was cooled to room temperature and excess xylenes removed on a rotary evaporator. The residual liquid product was further purified by heating under high vacuum to afford a viscous brown oily product (26.91 g). Elemental analyses for this PIB-SA-TEPA compound found C: 81.32%, H: 13.25%, N: 3.05%.
Example IE. Condensation of polypropylene succinic anhydride (PP-SA) with tetraethylenepentamine (TEPA)
[00104] A mixture of polypropylene succinic anhydride from Example IB (18.00 g,
20.77 mmol anhydride) and xylenes (50 ml) was stirred at room temperature under a nitrogen atmosphere and a solution of tetraethylenepentamine (3.15 g, 16.6 mmol) in xylenes (10 ml) was slowly added. The resulting mixture was heated in an oil bath at 175 °C for 24 hours. The brown mixture was cooled to room temperature and excess xylenes removed on a rotary evaporator. The residual liquid product was further purified by heating under high vacuum to afford a viscous brown oily product (20.52 g). Elemental analyses for this PP-SA-TEPA material found C: 78.30%, H: 12.97%, N: 5.11%.
Example IF. Condensation of propylene/l-hexene succinic anhydride (C3C6-SA) with tetraethylenepentamine (TEPA)
[00105] A mixture of propylene/l-hexene succinic anhydride Example 1C (25.70 g,
23.62 mmol anhydride) and xylenes (60 ml) was stirred at room temperature under a nitrogen atmosphere and a solution of tetraethylenepentamine (2.55 g, 13.5 mmol) in xylenes (15 ml) was slowly added. The resulting mixture was heated in an oil bath at 170 °C for 24 hours. The brown mixture was cooled to room temperature and excess xylenes removed on a rotary evaporator. The residual liquid product was further purified by heating under high vacuum to afford a viscous brown oily product (27.58 g). Elemental analyses for this C3C6-SA-TEPA material found C: 81.38%, H: 12.74%, N: 3.30%.
Example 1G. Maleation of vinyl- terminated atactic polypropylene
[00106] To a two-neck 500 ml round-bottomed flask equipped with an N2 inlet and a
N2 outlet was added vinyl-terminated atactic polypropylene (GPC Mw 5646, Mn 1474, 1H NMR Mn 1190.19 g/mol, 75.00 g, 63.02 mmol) followed by maleic anhydride (15.45 g, 157.56 mmol) at room temperature. The mixture was flushed with nitrogen for 10 min at room temperature and the mixture was heated to 190 °C (oil bath) for 63.5 hours under a nitrogen atmosphere. Additional maleic anhydride (3.10 g, 31.61 mmol) was added to the mixture that had been cooled to about 120 °C and heating was continued at 190 °C (oil bath) for an additional 17 hours under a nitrogen atmosphere. The mixture was cooled to room
temperature, diluted with hexanes, filtered and concentrated on a rotary evaporator. Excess maleic anhydride was removed by heating at 95 - 100 °C under high vacuum to afford a light brown viscous oily product (85.70 g). GPC Mw 4020, Mn 1413. Elemental analyses for this polypropylene succinic anhydride found C: 80.79%, H: 12.51%). The oxygen content of this material is estimated to be about 6.70 wt% by difference. The anhydride content of this polymer material is estimated to be about 1.396 mmol/g. Based on the molecular weight of polymer starting material, there is an average of 1.93 succinic anhydride functionality per polymer chain.
Example 1H. Maleation of vinyl-terminated atactic polypropylene
[00107] To a 300 ml stainless steel autoclave equipped with a mechanical stirrer and an N2 inlet and a N2 outlet was added vinyl-terminated atactic polypropylene (GPC Mw 2387, Mn 1069, 1H NMR Mn 1015.76 g/mol, 90 g, 88.60 mmol) followed by maleic anhydride (34.75 g, 354.37 mmol) at room temperature. The mixture was stirred and flushed three times with nitrogen at room temperature and pressurized to about 250 psi with nitrogen. The mixture was heated to 250 °C for 3 hours at about 400 psi and allowed to cool to room temperature. The pressure was released slowly and the autoclave was opened. The mixture was diluted with hexanes, filtered under house vacuum and the filtrate was concentrated on a rotary evaporator. Excess maleic anhydride was removed by heating at 95 °C under high vacuum to afford a light brown viscous oily product (100.92 g). GPC Mw 2527, Mn 1112. Elemental analyses for this polypropylene succinic anhydride found C: 77.92%, H: 11.77%. The oxygen content of this material is estimated to be about 10.31 wt% by difference. The anhydride content of this copolymer material is estimated to be about 2.148 mmol/g. Based on the molecular weight of polymer starting material, there is an average of about 2.76 succinic anhydride functionality per polymer chain.
Example 1J. Maleation of vinyl-terminated propylene/l-hexene copolymer
[00108] To a two-neck 500 ml round-bottomed flask equipped with a N2 inlet and an
N2 outlet was added vinyl-terminated propylene/l-hexene copolymer (GPC Mw 1259, Mn 889, 1H NMR Mn 846.53 g/mol, 150 g, 177.19 mmol) followed by maleic anhydride
(43.44 g, 442.99 mmol) at room temperature. The mixture was flushed with nitrogen for 10 min at room temperature and the mixture was heated to 190 °C (oil bath) for 38.5 hours under a nitrogen atmosphere. The mixture was cooled to room temperature, diluted with hexanes, filtered and concentrated on a rotary evaporator. Excess maleic anhydride was removed by heating at 95 - 100 °C under high vacuum to afford a light brown viscous oily product (178.94 g). GPC Mw 1587, Mn 1023. Elemental analyses for this propylene/1- hexene succinic anhydride copolymer found C: 80.01%, H: 12.15%. The oxygen content of this material is estimated to be about 7.84 wt% by difference. The anhydride content of this copolymer material is estimated to be about 1.633 mmol/g. Based on the molecular weight of polymer starting material, there is an average of about 1.65 succinic anhydride functionality per polymer chain.
Example IK. Maleation of vinyl-terminated propylene/l-hexene copolymer
[00109] To a 300 ml stainless steel autoclave equipped with a mechanical stirrer and an N2 inlet and a N2 outlet was added vinyl-terminated propylene/l-hexene copolymer (GPC Mw 1894, Mn 997, 1H NMR Mn 1012.79 g/mol, 90 g, 88.86 mmol) followed by maleic anhydride (20.91 g, 213.24 mmol) at room temperature. The mixture was stirred and flushed three times with nitrogen at room temperature and pressurized to about 80 psi with nitrogen. The mixture was heated to 250 °C for 3 hours at about 140 psi and allowed to cool to room temperature. The pressure was released slowly and the autoclave was opened. The mixture was diluted with hexanes, filtered under house vacuum and the filtrate was concentrated on a rotary evaporator. Excess maleic anhydride was removed by heating at 95 °C under high vacuum to afford a light brown viscous oily product (103.54 g). GPC Mw 1937, Mn 1058. Elemental analyses for this propylene/l-hexene succinic anhydride copolymer found C: 80.79%, H: 12.61%. The oxygen content of this material is estimated to be about 6.60 wt% by difference. The anhydride content of this copolymer material is estimated to be about 1.375 mmol/g. Based on the molecular weight of polymer starting material, there is an average of about 1.61 succinic anhydride functionality per polymer chain.
Example 1L. Maleation of vinyl-terminated propylene/l-butene copolymer
[00110] To a two-neck 250 ml round-bottomed flask equipped with a N2 inlet and an
N2 outlet was added vinyl-terminated propylene/l-butene copolymer (GPC Mw 2197, Mn 1030, 1H NMR Mn 1062.16 g/mol, 50 g, 47.07 mmol) followed by maleic anhydride (9.23 g, 94.13 mmol) at room temperature. The mixture was flushed with nitrogen for 10 min at room temperature and the mixture was heated to 190 °C (oil bath) for 84.5 hours under a nitrogen atmosphere. The mixture was cooled to room temperature, diluted with hexanes, filtered and concentrated on a rotary evaporator. Excess maleic anhydride was removed by heating at 95 - 100 °C under high vacuum to afford a light brown viscous oily product (54.97 g). The molecular weight of the product, Mw 2294, Mn 1242, determined by GPC. Elemental analyses for this propylene/l-butene succinic anhydride copolymer found C: 81.76%, H: 13.09%. The oxygen content of this material is estimated to be about 5.15 wt% by difference. The anhydride content of this copolymer material is estimated to be about 1.073 mmol/g. Based on the molecular weight of polymer starting material, there is an average of about 1.27 succinic anhydride functionality per polymer chain.
Example 1M. Condensation of polypropylene succinic anhydride with
tetraethylenepentamine (DMA4)
[00111] A mixture of polypropylene succinic anhydride (28.00 g, from Example 1G,
39.09 mmol anhydride) and xylenes (85 ml) was stirred at room temperature under a nitrogen atmosphere and a solution of tetraethylenepentamine (4.11 g, 21.71 mmol) in xylenes (15 ml) was slowly added. The resulting mixture was heated in an oil bath at 170 °C for 24 hours under a nitrogen atmosphere and an azeotropic mixture of xylenes and water was collected in a Dean-Stark trap. The light brown mixture was cooled to room
temperature and excess xylenes removed on a rotary evaporator. The residual liquid product was further purified by heating at 95 °C under high vacuum to afford a dark brown viscous product (28.21 g), whose Mw was determined to be 4738 by GPC. Elemental analyses for this PP-SA-TEPA material found C: 79.04%, H: 12.46%, N: 5.07%.
Example IN. Condensation of propylene/l-hexene succinic anhydride (C3C6-SA) with tetraethylenepentamine (TEPA)
[00112] A mixture of propylene/l-hexene succinic anhydride (30.00g, from Example
1 J, 48.99 mmol anhydride) and xylenes (85 ml) was stirred at room temperature under a nitrogen atmosphere and a solution of tetraethylenepentamine (4.22 g, 22.29 mmol) in xylenes (15 ml) was slowly added. The resulting mixture was heated in an oil bath at 165 °C for 24 hours under a nitrogen atmosphere and an azeotropic mixture of xylenes and water was collected in a Dean-Stark trap. The light brown mixture was cooled to room
temperature and excess xylenes removed on a rotary evaporator. The residual liquid product was further purified by heating at 95 °C under high vacuum to afford a brown viscous product (33.24 g), whose molecular weight Mw was determined to be 4684 by GPC.
Elemental analyses for this C3C6-SA-TEPA material found C: 77.96%, H: 12.11%, N:
4.46%.
Example IP. Condensation of propylene/l-butene succinic anhydride (C3C4-SA) with tetraethylenepentamine (TEPA)
[00113] A mixture of propylene/l-butene succinic anhydride (25.00 g, from Example
1L, 26.83 mmol anhydride) and xylenes (85 ml) was stirred at room temperature under a nitrogen atmosphere and a solution of tetraethylenepentamine (3.38 g, 17.86 mmol) in xylenes (15 ml) was slowly added. The resulting mixture was heated in an oil bath at 165 °C for 24 hours under a nitrogen atmosphere and an azeotropic mixture of xylenes and water was collected in a Dean-Stark trap. The light brown mixture was cooled to room
temperature and excess xylenes removed on a rotary evaporator. The residual liquid product was further purified by heating at 95 °C under high vacuum to afford a dark brown viscous product (27.57 g), whose molecular weight Mw was determined to be 3878 by GPC.
Elemental analyses for this C3C4-SA-TEPA material found C: 79.71%, H: 13.04%, N:
4.31%.
Example 1Q. Copolymerization of vinyl-terminated atactic polypropylene with maleic anhydride
[00114] A mixture of vinyl-terminated atactic polypropylene (NB# 25136-002-001,
GPC Mw 2301, Mn 1180, 1H NMR Mn 944.7 g/mol, 15.00 g, 15.88 mmol), maleic anhydride (2.49 g, 25.39 mmol) and xylenes (14 ml) was heated to 150 °C (oil bath temperature) under a nitrogen atmosphere. A solution of di-tert-butyl peroxide (0.244 g, 1.67 mmol) in xylenes (5 ml) was added slowly to the mixture over 1 hour while the oil bath was maintained at 150 °C. After complete addition of the peroxide solution, the mixture was heated at 155 °C for 4.5 hours and then at 160 °C for 1 hour under a nitrogen atmosphere. The mixture was cooled to room temperature and excess solvent and volatile material were removed on a rotary evaporator. The crude product was further purified by heating at 95 °C under high vacuum to afford a light yellow viscous material (17.26 g). The conversion of polypropylene starting material was about 81% according to 1H NMR spectroscopy. The molecular weight of the material was determined to be Mw 4247, Mn 1977 (by GPC). Elemental analyses for this PP-MA copolymer material found C: 81.01%, H: 12.56%. The oxygen content of this material is estimated to be about 6.43 wt% by difference. The anhydride content of this polymer material is estimated to be about 1.340 mmol/g.
Example 1R. Copolymerization of vinyl-terminated atactic polypropylene with maleic anhydride
[00115] A mixture of vinyl-terminated atactic polypropylene (GPC Mw 4453, Mn
2087, 1H NMR Mn 1751.5 g/mol, 30.00 g, 17.13 mmol), maleic anhydride (2.69 g, 27.43 mmol) and xylenes (17 ml) was heated to 148 °C (oil bath temperature) under a nitrogen atmosphere. A solution of di-tert-butyl peroxide (0.426 g, 2.91 mmol) in xylenes (5 ml) was added slowly to the mixture over 2 hours while the oil bath was maintained at 148 °C. After complete addition of the peroxide solution, the mixture was heated at 148 °C for 4.5 hours under a nitrogen atmosphere. Additional di-tert-butyl peroxide (0.15 g, 1.03 mmol) in xylenes (5 ml) was added to the mixture and heating was continued at 148 °C for an additional 4.5 hours. A further additional amount of di-tert-butyl peroxide (0.15 g, 1.03 mmol) in xylenes (5 ml) was added to the mixture and heating was continued at 148 °C for an additional 3.5 hours. The mixture was cooled to room temperature and excess solvent
and volatile material were removed on a rotary evaporator. The crude product was further purified by heating at 95 °C under high vacuum to afford a colorless viscous material (33.10 g). The conversion of polypropylene starting material was about 83% according to 1H NMR spectroscopy. The molecular weight of the material was determined as Mw 6552, Mn 2539 (by GPC). Elemental analyses for this PP-MA copolymer material found C: 82.89%, H: 13.10%. The oxygen content of this material is estimated to be about 4.01 wt% by difference. The anhydride content of this polymer material is estimated to be about 0.835 mmol/g.
Example IS. Copolymerization of vinyl-terminated propylene/l-hexene copolymer with maleic anhydride
[00116] A mixture of vinyl-terminated propylene/l-hexene copolymer (GPC Mw
3157, Mn 1453, 1H NMR Mn 1567.2 g/mol, 30.00 g, 19.14 mmol), maleic anhydride (3.75 g, 38.24 mmol) and xylenes (18 ml) was heated to 163 °C (oil bath temperature) under a nitrogen atmosphere. A solution of di-tert-butyl peroxide (0.560 g, 3.83 mmol) in xylenes (8 ml) was added slowly to the mixture over 80 minutes while the oil bath was maintained at 163 °C. After complete addition of the peroxide solution, the mixture was heated at 163 °C for 15.5 hours under a nitrogen atmosphere. The mixture was cooled to room temperature and excess solvent and volatile material were removed on a rotary evaporator. The crude product was further purified by heating at 95 °C under high vacuum to afford a light yellow viscous material (34.22 g). The conversion of propylene/l-hexene copolymer starting material was about 87% according to 1H NMR spectroscopy. Elemental analyses for this C3C6-MA copolymer material found C: 81.79%, H: 13.02%. The oxygen content of this material is estimated to be about 5.19 wt% by difference. The anhydride content of this polymer material is estimated to be about 1.081 mmol/g.
Example IT. Functionalization of polypropylene maleic anhydride copolymer with tetraethylenepentamine
[00117] A mixture of polypropylene/maleic anhydride (PP-MA) copolymer (6.00 g,
from Example 1Q, 8.04 mmol anhydride) and xylenes (45 ml) was stirred at room
temperature under a nitrogen atmosphere and a solution of tetraethylenepentamine (1.17 g, 6.18 mmol) in xylenes (5 ml) was slowly added. The resulting mixture was heated in an oil bath at 170 °C for 72 hours under a nitrogen atmosphere and an azeotropic mixture of xylenes and water was collected in a Dean-Stark trap. The light brown mixture was cooled to room temperature and excess xylenes removed on a rotary evaporator. The residual product was further purified by heating at 95 °C under high vacuum to afford a light brown viscous product (6.92 g). The molecular weight of this product was determined as Mw 4247, Mn 1302 (by GPC). Elemental analyses for this PP-MA-TEPA copolymer additive found C: 78.00%, H: 12.43%, N: 5.70%.
Example 1U. Functionalization of polypropylene-maleic anhydride copolymer with tetraethylenepentamine
[00118] A mixture of polypropylene/maleic anhydride (PP-MA) copolymer (8.00 g, from Example 1R, 6.68 mmol anhydride) and xylenes (55 ml) was stirred at room
temperature under a nitrogen atmosphere and a solution of tetraethylenepentamine (0.90 g, 4.75 mmol) in xylenes (5 ml) was slowly added. The resulting mixture was heated in an oil bath at 170 °C for 48 hours under a nitrogen atmosphere and an azeotropic mixture of xylenes and water was collected in a Dean-Stark trap. The light brown mixture was cooled to room temperature and excess xylenes removed on a rotary evaporator. The residual product was further purified by heating at 95 °C under high vacuum to afford a light brown viscous product (8.66 g), whose molecular weight Mw was determined to be 8440 by GPC. Elemental analyses for this PP-MA-TEPA copolymer additive found C: 80.47%, H: 12.92%, N: 3.62%.
Example IV. Functionalization of propylene/l-hexene-maleic anhydride copolymer with triethylenetetramine
[00119] A mixture of vinyl-terminated propylene/l-hexene-maleic anhydride (C3C6-
MA) copolymer (8.00 g, from Example IS, 8.65 mmol anhydride) and xylenes (55 ml) was stirred at room temperature under a nitrogen atmosphere and a solution of
triethylenetetramine (0.903 g, 6.18 mmol) in xylenes (5 ml) was slowly added. The resulting mixture was heated in an oil bath at 165 °C for 24 hours under a nitrogen atmosphere and an azeotropic mixture of xylenes and water was collected in a Dean-Stark trap. The light brown mixture was cooled to room temperature and excess xylenes removed on a rotary evaporator. The residual product was further purified by heating at 95 °C under high vacuum to afford a light brown viscous product (8.70 g), whose molecular weight Mw was determined to be 5690 by GPC. Elemental analyses for this C3C6-MA-TEPA
copolymer additive found C: 80.39%, H: 12.78%, N: 3.62%.
Example 1 W. Maleation of vinyl-terminated atactic polypropylene
[00120] To a two-neck 500 ml round-bottomed flask equipped with an N2 inlet and an
N2 outlet was added vinyl-terminated atactic polypropylene (GPC Mw 5087, Mn 2449, 1H NMR Mn 2009.73 g/mol, 190.00 g, 94.54 mmol) followed by maleic anhydride (27.81 g, 283.60 mmol) at room temperature. The mixture was flushed with nitrogen for 10 min at room temperature and the mixture was heated to 190 °C (oil bath) for 65 hours under a nitrogen atmosphere. The mixture was cooled to room temperature, diluted with hexanes, filtered and concentrated on a rotary evaporator. Excess maleic anhydride was removed by heating at 95 - 100 °C under high vacuum to afford a light brown viscous oily product (204.98 g). GPC Mw 5222, Mn 2459. Elemental analyses for this polypropylene succinic anhydride found C: 82.37%, H: 13.59%. The oxygen content of this material is estimated to be about 4.04 wt% by difference. The anhydride content of this polymer material is estimated to be about 0.842 mmol/g. Based on the molecular weight of polymer starting material, there is an average of 1.84 succinic anhydride functionality per polymer chain.
Example IX. Maleation of vinyl-terminated atactic polypropylene
[00121] To a two-neck 500 ml round-bottomed flask equipped with an N2 inlet and an
N2 outlet was added vinyl-terminated atactic polypropylene (GPC Mw 4694, Mn 2215, 1H NMR Mn 1880.45 g/mol, 150.00 g, 79.77 mmol) followed by maleic anhydride (31.28 g, 319.0 mmol) at room temperature. The mixture was flushed with nitrogen for 10 min at room temperature and the mixture was heated to 190 °C (oil bath) for 53 hours under a nitrogen atmosphere. The mixture was cooled to room temperature, diluted with hexanes, filtered and concentrated on a rotary evaporator. Excess maleic anhydride was removed by
heating at 95 - 100 °C under high vacuum to afford a light brown viscous oily product (163.5 g). GPC Mw 4387, Mn 2424. Elemental analyses for this polypropylene succinic anhydride found C: 81.58%, H: 13.00%. The oxygen content of this material is estimated to be about 5.42 wt% by difference. The anhydride content of this polymer material is estimated to be about 1.129 mmol/g. Based on the molecular weight of polymer starting material, there is an average of 2.39 succinic anhydride functionality per polymer chain.
Example 1Y. Condensation of polypropylene succinic anhydride with tetraethylenepentamine (DMA2)
[00122] A mixture of polypropylene succinic anhydride (28.00 g, from Example 1W,
23.58 mmol anhydride) and xylenes (85 ml) was stirred at room temperature under a nitrogen atmosphere and a solution of tetraethylenepentamine (3.19 g, 16.84 mmol) in xylenes (15 ml) was slowly added. The resulting mixture was heated in an oil bath at 170 °C for 24 hours under a nitrogen atmosphere and an azeotropic mixture of xylenes and water was collected in a Dean-Stark trap. The light brown mixture was cooled to room temperature and excess xylenes removed on a rotary evaporator. The residual liquid product was further purified by heating at 95 °C under high vacuum to afford a dark brown viscous product (30.41 g), whose Mw was determined to be 6075 by GPC. Elemental analyses for this PP-SA-TEPA material found C: 80.89%, H: 13.21%, N: 3.67%.
Example 1Z. Condensation of polypropylene succinic anhydride with tetraethylenepentamine (DMA3)
[00123] A mixture of polypropylene succinic anhydride (28.00 g, from Example IX,
31.61 mmol anhydride) and xylenes (70 ml) was stirred at room temperature under a nitrogen atmosphere and a solution of tetraethylenepentamine (3.99 g, 21.07 mmol) in xylenes (10 ml) was slowly added. The resulting mixture was heated in an oil bath at 170 °C for 24 hours under a nitrogen atmosphere and an azeotropic mixture of xylenes and water was collected in a Dean-Stark trap. The light brown mixture was cooled to room temperature and excess xylenes removed on a rotary evaporator. The residual liquid product was further purified by heating at 95 °C under high vacuum to afford a dark brown viscous
product (31.24 g), whose Mw was determined to be 5073 by GPC. Elemental analyses for this PP-SA-TEPA material found C: 80.46%, H: 13.16%, N: 4.48%.
Example 2 - Emulsion Treatment
Various examples of demulsification performed in accordance with the disclosed subject matter are provided herein. Polyisobutylene succinimide dispersants were obtained from commercial suppliers (Infineum, Lubrizol, Chevron Oronite, Afton Chemical, BASF, etc). Alternatively, polyisobutylene-based polyamine succinimide dispersants were prepared by using commercially available highly reactive polyisobutylenes (HR-PIB) from BASF and from Texas Petrochemcials (TPC) as exemplified below.
Example 2A: Control Experiment
[00124] 5.5 grams of water was added to a solution that consist of 96 cc hexadecane and 11 cc of 1166 ppm of Arab Light asphaltene in toluene before blending with a Waring blender for 30 seconds at 1/2 of the full power to produce a water- in-oil emulsion at room temperature. The emulsion was left in an Electrostatic Dehydration and Precipitation Tester (EDPT) (by Inter AV Inc.) transparent vessel at room temperature. An electric voltage of 3500 volts was then applied to the emulsion at an interval of 2 minutes. A visual observation of the amount of the water separated from the emulsion was made after an application of each voltage. No water separation was observed during these measurements. The variations in water separation with voltage applications are shown in Figure 2A (see the curve labeled with "without DMA"). The image of the transparent EDPT vessel after completion of the experiments is also shown in Figure 2B, right, labeled as "without DMA."
Example 2B
[00125] 5.5 grams of water was added to a solution that consist of 96 cc of hexadecane and 11 cc of 1166 ppm of Arab Light asphaltene in toluene and 62 ppm of a commercially available polyisobutylene succinic anhydride polyamine additive, PIB-SA- PAM-1 (DMA1), before blending with a Waring blender for 30 seconds at 1/2 of the full power to produce a water- in-oil emulsion at room temperature. The emulsion was left in an Electrostatic Dehydration and Precipitation Tester (EDPT) (from Inter AV Inc.) transparent
vessel at room temperature. An electric voltage of 3500 volts was then applied to the emulsion at an interval of 2 minutes. A visual observation of the amount of the water separated from the emulsion was made after an application of each voltage. Separation of water was observed after the first application of voltage. The variations in water separation with applications of voltage are shown in Figure 2A, the curve marked "with DMAl ." The image of the transparent EDPT vessel is shown in Figure 2B, left, labeled as "with DMAl ." As compared with the results in Example 2A, these results in Example 2B demonstrate that the addition of additive DMAl to oil can enhance electrocoalescence and emulsion resolution.
Example 2C
[00126] 50 cc of water and 97 cc of crude oil were heated to 85 °C. 4 cc of the preheated water was added to 90 cc of preheated crude oil and blended for 10 seconds at half full power using a Waring blender to generate a water-in-oil emulsion. 75 cc of an emulsion was then poured in a transparent vessel of an EDPT which was preheated to 90 °C. The vessel temperature was then increased to 120 °C.
[00127] Voltages of 500, 1500 and 3000 volts were applied at 10, 21, 33 minutes after the EDPT reached 120 °C, respectively. A voltage of 3000 volts was applied at 44, 55, 66 minutes after the EDPT reached 120 °C. The amount of water in the vessel which was separated from the crude was observed at 5, 16, 27, 39, 50, 61 and 72 minutes after the EDPT reached 120 °C. The variations in water separation with time and application of voltage are shown in Figure 3, labeled "Crude Emulsion without DMA." The maximum amount of water separated was 0.04 cc.
Example 2D
[00128] 50 cc of water and 97 cc of crude oil were heated to 85 °C. 100 ppm of DMAl, PIB-SA-PAM-1 (commercially obtained), was added to 90 cc of preheated crude oil and mixed well. 4 cc of the preheated water was then added to the said solution and blended for 10 seconds at half full power using a Waring blender to generate a water-in-oil emulsion. 75 cc of the emulsion was then poured in a transparent vessel of an EDPT which was preheated to 90 °C. The vessel temperature was then increased to 120 °C.
[00129] Voltages of 500, 1500 and 3000 volts were applied at 10, 21, 33 minutes after the EDPT reached 120 °C, respectively. A voltage of 3000 volts was applied at 44, 55, 66 minutes after the EDPT reached 120 °C. The amount of water in the vessel which was separated from the crude was observed at 5, 16, 27, 39, 50, 61 and 72 minutes after the EDPT reached 120 °C.
The variations in water separation with time and application of voltage are shown in Figure 3, labeled "Crude Emulsion with DMA1." The maximum amount of water separated was 0.70 cc.
Example 2E
[00130] 50 cc of water and 97 cc of crude oil were heated to 85 °C. 100 ppm of DMA2, PP-SA-TEPA-2 (from Example 1 Y), was added to 90 cc of preheated crude oil and mixed well. 4 cc of the preheated water was then added to the said solution and blended for 10 seconds at half full power using a Waring blender to generate a water- in-oil emulsion. 75 cc of the emulsion was then poured in a transparent vessel of an EDPT which was preheated to 90C. The vessel temperature was then increased to 120 °C. DMA2 will contain compounds according to Compound A and Compound B as disclosed above.
[00131] Voltages of 500, 1500 and 3000 volts were applied at 10, 21, 33 minutes after the EDPT reached 120 °C, respectively. A voltage of 3000 volts was applied at 44, 55, 66 minutes after the EDPT reached 120 °C. The amount of water in the vessel which was separated from the crude was observed at 5, 16, 27, 39, 50, 61 and 72 minutes after the EDPT reached 120 °C. The variations in water separation with time and application of voltage are shown in Figure 3, labeled "Crude Emulsion with DMA2." The maximum amount of water separated was 0.40 cc.
Example 2F
[00132] 50 cc of water and 97 cc of crude oil were heated to 85 °C. 100 ppm of DMA3, PP-SA-TEPA-3 (from Example 1Z), was added to 90 cc of preheated crude oil and mixed well. 4 cc of the preheated water was then added to the said solution and blended for 10 seconds at half full power using a Waring blender to generate a water- in-oil emulsion. 75
cc of the emulsion was then poured in a transparent vessel of an EDPT which was preheated to 90 °C. The vessel temperature was then increased to 120 °C. DMA3 will contain compounds according to Compound A and Compound B as disclosed above.
[00133] Voltages of 500, 1500 and 3000 volts were applied at 10, 21, 33 minutes after the EDPT reached 120 °C, respectively. A voltage of 3000 volts was applied at 44, 55, 66 minutes after the EDPT reached 120 °C. The amount of water in the vessel which was separated from the crude was observed at 5, 16, 27, 39, 50, 61 and 72 minutes after the EDPT reached 120° C. The variations in water separation with time and application of voltage are shown in Figure 3, labeled "Crude Emulsion with DMA3." The maximum amount of water separated was 1.00 cc.
Example 2G
[00134] 50 cc of water and 97 cc of crude oil were heated to 85 °C. 100 ppm of DMA4, PP-SA-TEPA-4 (from Example 1M), was added to 90 cc of preheated crude oil and mixed well. 4 cc of the preheated water was then added to the said solution and blended for 10 seconds at half full power using a Waring blender to generate a water- in-oil emulsion. 75 cc of the emulsion was then poured in a transparent vessel of an EDPT which was preheated to 90 °C. The vessel temperature was then increased to 120 °C. DMA4 will contain compounds according to Compound A and Compound B as disclosed above.
[00135] Voltages of 500, 1500 and 3000 volts were applied at 10, 21, 33 minutes after the EDPT reached 120 °C, respectively. A voltage of 3000 volts was applied at 44, 55, 66 minutes after the EDPT reached 120 °C. The amount of water in the vessel which was separated from the crude was observed at 5, 16, 27, 39, 50, 61 and 72 minutes after the EDPT reached 120 °C.
The variations in water separation with time and application of voltage are shown in Figure 3, labeled "Crude Emulsion with DMA4." The maximum amount of water separated was 1.20 cc.
Additional Embodiments
[00136] Additionally or alternatively, the presently disclosed subject matter can include one or more of the following embodiments.
[00137] Embodiment 1 : A method for treating an emulsion of a hydrocarbon, comprising (i) providing an emulsion of a crude hydrocarbon; (ii) adding an additive to the emulsion to obtain a treated hydrocarbon, the additive being represented by one of Formula A, B, C, and D below:
(Formula A)
wherein in each of the Formula A, B, C, and D above: m is an integer between 0 and 10 inclusive; Ri is a branched or straight-chained Cio-Cgoo alkyl or alkenyl group; R2 is a C1-C4 branched or straight chained alkylene group; R3 is a C1-C4 branched or straight chained alkylene group; R31 is hydrogen or -R8-R , wherein R8 is C1-C4 branched or straight chained alkylene group, and R9 is
wherein R91 is a branched or straight-chained Cio-Cgoo alkyl or alkenyl group; or R8 and R9 together are a C1-C4 branched or straight chained alkyl group optionally substituted with one or more amine groups; and further wherein the -N(R3i)-R3- repeat unit is optionally interrupted in one or more places by a nitrogen-containing heterocyclic cycloalkyl group; and R4 and R5 are each independently selected from (a) hydrogen; (b) a bond connected to R3i in the last distal -N(R3i)-R3- repeat unit; or (c) -R6-R7, wherein R<5 is C1-C4 branched or straight chained alkylene group, and R7 is
wherein R7i is a branched or straight-chained Cio-Csoo alkyl or alkenyl group; wherein in Formula B, n is an integer between 0 and 10 inclusive, and the groups R2', R3 ', R3i ' , R4' and R5 ' are each defined the same as R2, R3, R3i and R4, and R5, respectively; wherein in Formula D, z is 1 or 2, and y is an integer between 1 and 5 inclusive.
[00138] Embodiment 2: The method of embodiment 1, wherein at least one of Ri,
R7i, and R91 comprises polypropylene.
[00139] Embodiment 3: The method of embodiment 2, wherein the polypropylene is atactic polypropylene, isotactic polypropylene, or syndiotactic polypropylene.
[00140] Embodiment 4: The method of embodiment 2, wherein the polypropylene is amorphous.
[00141] Embodiment 5: The method of embodiment 2, wherein the polypropylene includes isotactic or syndiotactic crystallizable units.
[00142] Embodiment 6: The method of embodiment 2, wherein the polypropylene includes meso diads constituting from about 30% to about 99.5% of the total diads of the polypropylene.
[00143] Embodiment 7: The method of embodiment 2, wherein at least one of
Ri, R71, and R91 has a number-averaged molecular weight of from about 300 to about 30000 g/mol.
[00144] Embodiment 8: The method of embodiment 2, wherein at least one of
Ri, R71, and R91 has a number-averaged molecular weight of from about 500 to about 5000 g/mol.
[00145] Embodiment 9: The method of embodiment 1 , wherein at least one of
Ri, R71, and R91 comprises polyethylene.
[00146] Embodiment 10: The method of embodiment 1 , wherein at least one of
Ri, R71, and R91 comprises poly(ethylene-co-propylene).
[00147] Embodiment 1 1 : The method of embodiment 10, wherein at least one of
Ri, R71, and R91 comprises from about 1 mole % to about 90 mole % of ethylene units and from about 99 mole % to about 10 mole% propylene units.
[00148] Embodiment 12: The method of embodiment 1 1 , wherein at least one of
Ri, R71, and R91 comprises from about 10 mole % to about 50 mole % of ethylene units.
[00149] Embodiment 13 : The method of embodiment 1 , wherein at least one of
Ri, R71, and R91 comprises poly(higher alpha-olefm), the higher alpha-olefm including two or more carbon atoms on each side chain.
[00150] Embodiment 14: The method of embodiment 1 , wherein at least one of
Ri, R71, and R91 comprises poly(propylene-co-higher alpha-olefm), the higher alpha-olefm including two or more carbon atoms on each side chain.
[00151] Embodiment 15: The method of any one of the previous embodiments, wherein the nitrogen content in the compound is about 1 wt% to about 10 wt% based on the total weight of the compound.
[00152] Embodiment 16. The method of any one of the previous embodiments, wherein R3 is -CH2-CH2-, and R3i is hydrogen.
[00153] Embodiment 17. The method of embodiment 16, wherein the -N(R3i)-
R3- repeat unit is interrupted in one or more places by a 1,4-diethylenediamine.
[00154] Embodiment 18. The method of any one of the previous embodiments, wherein the treated hydrocarbon is in a hydrocarbon phase as a result of demulsification of the emulsion.
[00155] The disclosed subject matter is not to be limited in scope by the specific embodiments described herein. Indeed, various modifications of the invention in addition to those described herein will become apparent to those skilled in the art from the foregoing description and the accompanying figures. Such modifications are intended to fall within the scope of the appended claims.
[00156] It is further to be understood that all values are approximate, and are provided for description.
[00157] Patents, patent applications, publications, product descriptions, and protocols are cited throughout this application, the disclosures of each of which is incorporated herein by reference in its entirety for all purposes.
* * *
Claims
1 : A method for treating an emulsion of a hydrocarbon, comprising (i) providing an emulsion of a crude hydrocarbon; (ii) adding an additive to the emulsion to obtain a treated hydrocarbon, the additive being represented by one of Formula A, B, C, and D below:
(Formula A)
wherein in each of the Formula A, B, C, and D above: m is an integer between 0 and 10 inclusive; Ri is a branched or straight-chained Cio-Cgoo alkyl or alkenyl group; R2 is a C1-C4 branched or straight chained alkylene group; R3 is a C1-C4 branched or straight chained alkylene group; R31 is hydrogen or -R8-R , wherein R8 is C1-C4 branched or straight chained alkylene group, and R9 is
wherein R91 is a branched or straight-chained Cio-Cgoo alkyl or alkenyl group; or R8 and R9 together are a C1-C4 branched or straight chained alkyl group optionally substituted with one or more amine groups; and further wherein the -N(R3i)-R3- repeat unit is optionally interrupted in one or more places by a nitrogen-containing heterocyclic cycloalkyl group; and R4 and R5 are each independently selected from (a) hydrogen; (b) a bond connected to R3i in the last distal -N(R3i)-R3- repeat unit; or (c) -R6-R7, wherein R<5 is C1-C4 branched or straight chained alkylene group, and R7 is
wherein R7i is a branched or straight-chained Cio-Csoo alkyl or alkenyl group; wherein in Formula B, n is an integer between 0 and 10 inclusive, and the groups R2', R3 ', R3i ' , R4' and R5 ' are each defined the same as R2, R3, R3i and R4, and R5, respectively; wherein in Formula D, z is 1 or 2, and y is an integer between 1 and 5 inclusive.
2: The method of claim 1, wherein at least one of Ri, R71, and R91 comprises polypropylene.
3: The method of claim 2, wherein the polypropylene is atactic polypropylene, isotactic polypropylene, or syndiotactic polypropylene.
4: The method of claim 2, wherein the polypropylene is amorphous.
5: The method of claim 2, wherein the polypropylene includes isotactic or syndiotactic crystallizable units.
6: The method of claim 2, wherein the polypropylene includes meso diads constituting from about 30% to about 99.5% of the total diads of the polypropylene.
7: The method of claim 2, wherein at least one of Rl s R71, and R91 has a number- averaged molecular weight of from about 300 to about 30000 g/mol.
8: The method of claim 2, wherein at least one of Rl s R71, and R91 has a number- averaged molecular weight of from about 500 to about 5000 g/mol.
9: The method of claim 1, wherein at least one of Rl s R71, and R91 comprises polyethylene.
10: The method of claim 1, wherein at least one of Rl s R71, and R91 comprises poly(ethylene-co-propylene) .
11 : The method of claim 10, wherein at least one of Ri, R71, and R91 comprises from about 1 mole % to about 90 mole % of ethylene units and from about 99 mole % to about 10 mole% propylene units.
12: The method of claim 11, wherein at least one of Ri, R71, and R91 comprises from about 10 mole % to about 50 mole % of ethylene units.
13: The method of claim 1, wherein at least one of Rl s R71, and R91 comprises poly (higher alpha-olefin), the higher alpha-olefin including two or more carbon atoms on each side chain.
14: The method of claim 1, wherein at least one of Ri, R71, and R91 comprises poly(propylene-co-higher alpha-olefin), the higher alpha-olefin including two or more carbon atoms on each side chain.
15: The method of any one of the previous claims, wherein the nitrogen content in the compound is about 1 wt% to about 10 wt% based on the total weight of the compound.
16. The method of any one of the previous claims, wherein R3 is -CH2-CH2-, and R3i is hydrogen.
17. The method of claim 16, wherein the -N(R3i)-R3- repeat unit is interrupted in one or more places by a 1 ,4-diethylenediamine.
18. The method of any one of the previous claims, wherein the treated hydrocarbon is in a hydrocarbon phase as a result of demulsification of the emulsion.
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US13/804,507 US9085737B2 (en) | 2013-03-14 | 2013-03-14 | Functionalized polymers containing polyamine succinimide for demulsification in hydrocarbon refining processes |
US13/804,507 | 2013-03-14 |
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EP1910504B1 (en) * | 2005-08-03 | 2019-01-30 | Innospec Limited | Fuel additives for lubricity improvement |
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US9085737B2 (en) | 2015-07-21 |
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